WO2023024164A1 - Glass ceramic, and preparation method therefor and use thereof - Google Patents

Abstract

A glass-ceramic comprising a glass substrate and a composite glass-ceramic layer covering the surface of the glass substrate, wherein the composite glass-ceramic layer comprises beta-spodumene of hexagonal crystal form, beta-spodumene of tetragonal crystal form and other glass. The surface of the glass-ceramic has very high Vickers hardness and compressive stress, such that the surface hardness and the drop resistance of the glass are significantly improved, and the glass is easy to process and has a low cost.

Description

Glass-ceramic and its preparation method and application technical field

The invention relates to the field of glass, in particular to a glass-ceramic and its preparation method and application.

Background technique

With the rapid development of the smart technology industry and the popularization of digital products in recent years, smart phones and tablet computers equipped with touch screens have become an indispensable part of people's lives. Strength "Armor". The cover material of the traditional touch screen is mainly high-alumina glass, which is mainly used in the outermost layer of the touch screen. It has the functions of impact resistance, scratch resistance, oil resistance, fingerprint resistance, and enhanced light transmittance. At present, high alumina glass is widely used in various electronic consumer products with touch function and display function.

Traditional technology has developed high-aluminosilicate glass and lithium-aluminosilicate glass by increasing the alumina content and adding lithium oxide, etc., and through one or more chemical strengthening to improve the impact resistance, scratch resistance, Anti-drop, anti-sweat erosion and other properties. However, due to the inherent brittleness and low crack growth resistance of glass materials, its drop resistance performance on rough ground is largely limited, especially the multiple drop resistance performance, which is usually lower than 1.4 meters; and its Vickers hardness It is often between 550Kgf/mm ² and 680Kgf/mm ² , and it is difficult to exceed 700Kgf/mm ² , that is, the scratch resistance is weak.

There is also a traditional technique to prepare a high-strength glass-ceramic with lithium feldspar and lithium silicate structure, which is a kind of glass-ceramics with integral devitrification, which has high mechanical strength and fracture resistance. However, it contains more than 10wt% of Li ₂ O. Due to the limited reserves of Li ₂ O, its cost has remained high all year round, resulting in very high cost of the glass-ceramic, which is more than 10 times higher than that of similar lithium-aluminosilicate glass; and because it is The overall crystallization is similar to ceramics in the glass post-processing process, and the processing difficulty and cost are much higher than that of glass substrates.

Contents of the invention

Based on this, the present invention provides a glass-ceramic, which forms a composite glass-ceramic layer containing a β-spodumene crystal phase on the surface of the glass substrate, and the surface of the glass-ceramic has a very high Vickers hardness And compressive stress, thereby significantly improving the surface hardness and drop resistance of the glass, while being easy to process and low in cost.

The present invention is realized through the following technical solutions.

A glass-ceramic, the glass-ceramic comprising a glass substrate and a composite glass-ceramic layer coated on the surface of the glass substrate;

Wherein, the composite glass-ceramics layer includes hexagonal β-spodumene, tetragonal β-spodumene and other glasses.

In one embodiment, in terms of mass percentage, the composite glass-ceramics layer includes 19.2% to 88.5% of the hexagonal β-spodumene, 3% to 75.8% of the tetragonal β-spodumene β-spodumene and 5%-14.8% of the other glasses mentioned above.

In one embodiment, the other glasses include SiO ₂ , Al ₂ O ₃ , Li ₂ O, Na ₂ O and other oxides; the other oxides are selected from K ₂ O, MgO, ZrO ₂ , B ₂ At least three of O ₃ , P ₂ O ₅ and ZnO; and/or

The glass matrix includes SiO ₂ , Al ₂ O ₃ , Li ₂ O, Na ₂ O and other oxides; the other oxides are selected from K ₂ O, MgO, ZrO ₂ , B ₂ O ₃ , P ₂ O ₅ with at least three of ZnO.

In one embodiment, the thickness of the composite glass-ceramic layer is 2 μm˜90 μm.

The present invention also provides a method for preparing the above-mentioned glass-ceramics, comprising the following steps:

Preparing a glass preform, subjecting the glass preform to first crystallization and second crystallization to prepare the composite glass-ceramic layer;

Among them, the temperature for the first crystallization is 630°C-700°C, and the time for the first crystallization is 2h-10h;

After the first crystallization is completed, the temperature is raised to carry out the second crystallization, the temperature of the second crystallization is 780°C-830°C, and the time of the second crystallization is 0.5h-4h.

In one embodiment, the raw materials of the glass preform are mixed, melted at 1500°C-1650°C for 7h-9h, then lowered to 1300°C-1500°C, kept for 1.5h-2.5h, and shaped to prepare glass block, annealing and cooling after the glass block is hardened;

Wherein, the raw material of the glass preform includes SiO ₂ , Al ₂ O ₃ , Li ₂ O, Na ₂ O and other oxides; the other oxides are selected from K ₂ O, MgO, ZrO ₂ , B ₂ O ₃ , P ₂ O ₅ and ZnO at least three.

In one embodiment, in terms of mass percentage, the raw materials of the glass preform include 50%-68% SiO ₂ , 18%-29.5% Al ₂ O ₃ , 2%-6.5% Li ₂ O, 3%- 10% Na ₂ O and 0.1%-15% of other oxides.

In one embodiment, the temperature of the first crystallization is 660°C-700°C, and the time of the first crystallization is 2h-10h.

In one embodiment, the temperature of the second crystallization is 810°C-830°C, and the time of the second crystallization is 1h-4h.

In one embodiment, the heating rate is 2°C/min˜10°C/min.

The present invention also provides the application of the above-mentioned glass-ceramic in protective glass, special glass and architectural glass of electronic devices.

Compared with the prior art, the glass-ceramic of the present invention has the following beneficial effects:

The glass-ceramic of the present invention includes a glass substrate, and a composite glass-ceramic layer containing β-spodumene crystal phase and other glasses formed on the surface of the glass substrate, wherein the β-spodumene includes hexagonal With tetragonal crystal form. This composite glass-ceramic layer can form a uniform and dense compressive stress layer on the glass surface, making it have very high Vickers hardness and compressive stress, thereby significantly improving the surface hardness and drop resistance of the entire glass.

In addition, the crystallized glass of the present invention maintains the advantages of easy processing of the glass base material, has low cost and is easy to be industrialized.

Description of drawings

Fig. 1 is the XRD collection of illustrative plates of the sample provided by the present invention; Wherein: 1 represents the XRD collection of illustrative plates of the composite glass-ceramic layer of the glass-ceramics preform that embodiment 6 provides, and 2 represents the composite crystallite of the glass-ceramic preform that embodiment 12 provides The XRD collection of illustrative plates of glass layer, 3 represent the XRD collection of illustrative plates of the composite glass-ceramics layer of glass-ceramics preform that embodiment 1 provides, 4 represent the XRD collection of illustrative plates of the β-spodumene sample of hexagonal crystal form, 5 represent the β-spodumene of tetragonal crystal form - the XRD pattern of the spodumene sample;

Fig. 2 is a scanning electron micrograph of a cross-section of a sample provided by Example 2 of the present invention.

Detailed ways

In order to facilitate understanding of the present invention, the present invention will be described more fully below with reference to related examples. Preferred embodiments of the invention are given in the examples. However, the present invention can be embodied in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the understanding of the disclosure of the present invention more thorough and comprehensive.

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the technical field of the invention. The terminology used herein in the description of the present invention is only for the purpose of describing specific embodiments, and is not intended to limit the present invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.

The invention provides a glass-ceramic, which comprises a glass substrate and a composite glass-ceramic layer coated on the surface of the glass substrate;

Wherein, the composite glass-ceramic layer includes hexagonal β-spodumene, tetragonal β-spodumene and other glasses.

In a specific example, in terms of mass percentage, the composite glass-ceramic layer includes 19.2% to 88.5% of hexagonal β-spodumene, 3% to 75.8% of tetragonal β-spodumene and 5% to 14.8% of other glass.

In glass-ceramics, the components of other glasses are the same as those of the glass matrix.

In a specific example, other glasses include SiO ₂ , Al ₂ O ₃ , Li ₂ O, Na ₂ O and other oxides; other oxides are selected from K ₂ O, MgO, ZrO ₂ , B ₂ O ₃ , P At least three of ₂ O ₅ and ZnO.

In a specific example, the glass matrix includes SiO ₂ , Al ₂ O ₃ , Li ₂ O, Na ₂ O and other oxides; other oxides are selected from K ₂ O, MgO, ZrO ₂ , B ₂ O ₃ , P At least three of ₂ O ₅ and ZnO.

In a specific example, the composite glass-ceramic layer has a thickness of 2 μm˜90 μm. It can be understood that in the present invention, the thickness of the composite glass-ceramic layer includes but is not limited to 2 μm, 3 μm, 4 μm, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm.

The present invention also provides a method for preparing the above-mentioned glass-ceramics, comprising the following steps:

Prepare a glass preform, perform the first crystallization and the second crystallization on the glass preform, and prepare a composite glass-ceramic layer;

Among them, the temperature for the first crystallization is 630°C-700°C, and the time for the first crystallization is 2h-10h;

After the first crystallization is completed, the temperature is raised to carry out the second crystallization, the temperature of the second crystallization is 780°C-830°C, and the time of the second crystallization is 0.5h-4h.

After the glass preform undergoes two specific crystallization processes, a layer will be uniformly deposited on the surface layer, that is, the composite glass-ceramic layer, and the remaining unprecipitated layer is the intermediate glass layer. The composite glass-ceramic layer and the glass layer together form a glass-ceramic .

In a specific example, preparing the glass preform includes the following steps: mixing the raw materials of the glass preform, melting at 1500°C to 1650°C for 7h to 9h, then lowering the temperature to 1300°C to 1500°C, and keeping the temperature for 1.5h to 2.5 h, molding, preparing a glass block, annealing and cooling after the glass block is hardened;

Among them, the raw materials of the glass preform include SiO ₂ , Al ₂ O ₃ , Li ₂ O, Na ₂ O and other oxides; other oxides are selected from K ₂ O, MgO, ZrO ₂ , B ₂ O ₃ , P ₂ O ₅ and at least three of ZnO.

It can be understood that in the present invention, any substance containing SiO ₂ , Al ₂ O ₃ , Li ₂ O, Na ₂ O and other oxides can be used as raw materials, including but not limited to: quartz sand, aluminum hydroxide, Lithium Carbonate/Spodumene, Sodium Carbonate, Sodium Nitrate.

In a specific example, in terms of mass percentage, the raw materials of the glass preform include 50%-68% SiO ₂ , 18%-29.5% Al ₂ O ₃ , 2%-6.5% Li ₂ O, 3%-10% Na ₂ O and 0.1% to 15% of other oxides.

Preferably, the temperature of the first crystallization is 660°C-700°C.

Preferably, the time for the first crystallization is 2h-10h.

Preferably, the temperature of the second crystallization is 810°C-830°C.

Preferably, the time for the second crystallization is 1 h to 4 h.

In a specific example, the heating rate is 2°C/min˜10°C/min. It can be understood that in the present invention, the heating rate includes but not limited to 2°C/min, 3°C/min, 4°C/min, 5°C/min, 6°C/min, 7°C/min, 8°C/min , 9°C/min, 10°C/min.

The present invention also provides the application of the above-mentioned glass-ceramic in protective glass, special glass and architectural glass of electronic devices. Understandably, electronic devices include but are not limited to smart display devices, mobile devices, and the like.

It can be understood that in the present invention, the glass-ceramics mentioned above can be obtained in the traditional flat glass manufacturing process, and the manufacturing process is not limited to the float forming process, overflow down-draw method, lead-up method, flat-drawing method, calendering method, etc. .

The glass-ceramic and its preparation method of the present invention will be further described in detail below in conjunction with specific examples. The raw materials used in the following examples, unless otherwise specified, are commercially available products.

Example 1

The present embodiment provides a glass-ceramic and a preparation method thereof, specifically as follows:

Step 1: Preparation of glass preforms

In terms of mass percentage, the following raw materials are mixed:

58% SiO ₂ , 22% Al ₂ O ₃ , 0.5% K ₂ O, 1.5% MgO, 10% Na ₂ O, 4% Li ₂ O, 2% ZrO ₂ , 1% B ₂ O ₃ , 1% ZnO;

After fully mixing evenly, use a platinum crucible to melt at 1500-1650°C for 8 hours, and at the same time stir with a platinum stirring paddle. After the stirring paddle is pulled out, cool down to 1300-1500°C, keep warm for 2 hours and homogenize, and cast it on an iron mold to form For glass blocks with a size of about 80*160mm, preheat to 450°C before casting the mold. After the glass blocks are hardened, immediately transfer them to an annealing furnace for annealing, keep them warm for 2 hours, then cool down to 140°C for 6 hours, cool naturally, and take them out for later use.

Step 2: Preparation of glass-ceramics

The above-mentioned glass preform is crystallized according to the following crystallization process, wherein TT1 refers to the time and temperature of the first crystallization process, and TT2 refers to the time and temperature of the second crystallization process:

TT1: 645°C, 4h;

TT2: 800°C, 1h;

The heating rate is 10°C/min.

Example 2

The present embodiment provides a glass-ceramic and a preparation method thereof, specifically as follows:

Step 1: Preparation of glass preforms

In terms of mass percentage, the following raw materials are mixed:

58% SiO ₂ , 20% Al ₂ O ₃ , 4% K ₂ O, 4% MgO, 4.5% Na ₂ O, 5% Li ₂ O, 4.5% ZrO ₂ ;

After fully mixing evenly, use a platinum crucible to melt at 1500-1650°C for 8 hours, and at the same time stir with a platinum stirring paddle. After the stirring paddle is pulled out, cool down to 1300-1500°C, keep warm for 2 hours and homogenize, and cast it on an iron mold to form For glass blocks with a size of about 80*160mm, preheat to 450°C before casting the mold. After the glass blocks are hardened, immediately transfer them to an annealing furnace for annealing, keep them warm for 2 hours, then cool down to 140°C for 6 hours, cool naturally, and take them out for later use.

Step 2: Preparation of glass-ceramics

The above-mentioned glass preform is crystallized according to the following crystallization process, wherein TT1 refers to the time and temperature of the first crystallization process, and TT2 refers to the time and temperature of the second crystallization process:

TT1: 630℃, 6h;

TT2: 810°C, 1h;

The heating rate was 5°C/min.

Example 3

The present embodiment provides a glass-ceramic and a preparation method thereof, specifically as follows:

Step 1: Preparation of glass preforms

In terms of mass percentage, the following raw materials are mixed:

56% SiO ₂ , 26% Al ₂ O ₃ , 1% K ₂ O, 1.5% MgO, 2% Na ₂ O, 7% Li ₂ O, 1% ZrO ₂ , 1% B ₂ O ₃ , 0.5% P ₂ O ₅ , 4% ZnO;

After fully mixing evenly, use a platinum crucible to melt at 1500-1650°C for 8 hours, and at the same time stir with a platinum stirring paddle. After the stirring paddle is pulled out, cool down to 1300-1500°C, keep warm for 2 hours and homogenize, and cast it on an iron mold to form For glass blocks with a size of about 80*160mm, preheat to 450°C before casting the mold. After the glass blocks are hardened, immediately transfer them to an annealing furnace for annealing, keep them warm for 2 hours, then cool down to 140°C for 6 hours, cool naturally, and take them out for later use.

Step 2: Preparation of glass-ceramics

The above-mentioned glass preform is crystallized according to the following crystallization process, wherein TT1 refers to the time and temperature of the first crystallization process, and TT2 refers to the time and temperature of the second crystallization process:

TT1: 680℃, 4h;

TT2: 810°C, 1h;

The heating rate is 2°C/min.

Example 4

The present embodiment provides a glass-ceramic and a preparation method thereof, specifically as follows:

Step 1: Preparation of glass preforms

In terms of mass percentage, the following raw materials are mixed:

61% SiO ₂ , 23% Al ₂ O ₃ , 1.3% K ₂ O, 1.5% MgO, 4.2% Na ₂ O, 3.5% Li ₂ O, 1% ZrO ₂ , 3% B ₂ O ₃ , 0.5% P ₂ O ₅ , 1% ZnO;

After fully mixing evenly, use a platinum crucible to melt at 1500-1650°C for 8 hours, and at the same time stir with a platinum stirring paddle. After the stirring paddle is pulled out, cool down to 1300-1500°C, keep warm for 2 hours and homogenize, and cast it on an iron mold to form For glass blocks with a size of about 80*160mm, preheat to 450°C before casting the mold. After the glass blocks are hardened, immediately transfer them to an annealing furnace for annealing, keep them warm for 2 hours, then cool down to 140°C for 6 hours, cool naturally, and take them out for later use.

Step 2: Preparation of glass-ceramics

The above-mentioned glass preform is crystallized according to the following crystallization process, wherein TT1 refers to the time and temperature of the first step of the crystallization process, and TT2 refers to the time and temperature of the second step of the crystallization process:

TT1: 650℃, 10h;

TT2: 800°C, 2h;

The heating rate is 10°C/min.

Example 5

The present embodiment provides a glass-ceramic and a preparation method thereof, specifically as follows:

Step 1: Preparation of glass preforms

In terms of mass percentage, the following raw materials are mixed:

68% SiO ₂ , 18% Al ₂ O ₃ , 1% K ₂ O, 1.5% MgO, 4% Na ₂ O, 4.5% Li ₂ O, 1% ZrO ₂ , 1.5% B ₂ O ₃ , 0.5% P ₂ O ₅ ;

After fully mixing evenly, use a platinum crucible to melt at 1500-1650°C for 8 hours, and at the same time stir with a platinum stirring paddle. After the stirring paddle is pulled out, cool down to 1300-1500°C, keep warm for 2 hours and homogenize, and cast it on an iron mold to form For glass blocks with a size of about 80*160mm, preheat the mold to 450°C before casting the mold. After the glass block is hardened, immediately transfer it to an annealing furnace for annealing, keep it warm for 2 hours, then cool down to 140°C for 6 hours, cool naturally, and take it out for later use.

Step 2: Preparation of glass-ceramics

The above-mentioned glass preform is crystallized according to the following crystallization process, wherein TT1 refers to the time and temperature of the first crystallization process, and TT2 refers to the time and temperature of the second crystallization process:

TT1: 660°C, 4h;

TT2: 810°C, 1h;

The heating rate was 5°C/min.

Example 6

The present embodiment provides a glass-ceramic and a preparation method thereof, specifically as follows:

Step 1: Preparation of glass preforms

In terms of mass percentage, the following raw materials are mixed:

59% SiO ₂ , 25% Al ₂ O ₃ , 1% K ₂ O, 1.5% MgO, 3% Na ₂ O, 2% Li ₂ O, 0.5% ZrO ₂ , 3% B ₂ O ₃ , 5% P ₂ O ₅ ;

After fully mixing evenly, use a platinum crucible to melt at 1500-1650°C for 8 hours, and at the same time stir with a platinum stirring paddle. After the stirring paddle is pulled out, cool down to 1300-1500°C, keep warm for 2 hours and homogenize, and cast it on an iron mold to form For glass blocks with a size of about 80*160mm, preheat to 450°C before casting the mold. After the glass blocks are hardened, immediately transfer them to an annealing furnace for annealing, keep them warm for 2 hours, then cool down to 140°C for 6 hours, cool naturally, and take them out for later use.

Step 2: Preparation of glass-ceramics

The above-mentioned glass preform is crystallized according to the following crystallization process, wherein TT1 refers to the time and temperature of the first crystallization process, and TT2 refers to the time and temperature of the second crystallization process:

TT1: 675°C, 4h;

TT2: 795°C, 1h;

The heating rate is 10°C/min.

Example 7

The present embodiment provides a glass-ceramic and a preparation method thereof, specifically as follows:

Step 1: Preparation of glass preforms

In terms of mass percentage, the following raw materials are mixed:

58% SiO ₂ , 22% Al ₂ O ₃ , 1% K ₂ O, 1% MgO, 3% Na ₂ O, 6% Li ₂ O, 2% ZrO ₂ , 3% B ₂ O ₃ , 2% P ₂ O ₅ , 2% ZnO;

After fully mixing evenly, use a platinum crucible to melt at 1500-1650°C for 8 hours, and at the same time stir with a platinum stirring paddle. After the stirring paddle is pulled out, cool down to 1300-1500°C, keep warm for 2 hours and homogenize, and cast it on an iron mold to form For glass blocks with a size of about 80*160mm, preheat to 450°C before casting the mold. After the glass blocks are hardened, immediately transfer them to an annealing furnace for annealing, keep them warm for 2 hours, then cool down to 140°C for 6 hours, cool naturally, and take them out for later use.

Step 2: Preparation of glass-ceramics

The above-mentioned glass preform is crystallized according to the following crystallization process, wherein TT1 refers to the time and temperature of the first crystallization process, and TT2 refers to the time and temperature of the second crystallization process:

TT1: 690°C, 4h;

TT2: 820°C, 1h;

The heating rate is 2°C/min.

Example 8

The present embodiment provides a glass-ceramic and a preparation method thereof, specifically as follows:

Step 1: Preparation of glass preforms

In terms of mass percentage, the following raw materials are mixed:

50% SiO ₂ , 29.5% Al ₂ O ₃ , 1.4% K ₂ O, 0.5% MgO, 7% Na ₂ O, 4% Li ₂ O, 1% ZrO ₂ , 5% B ₂ O ₃ , 1.6% P ₂ O ₅ ;

After fully mixing evenly, use a platinum crucible to melt at 1500-1650°C for 8 hours, and at the same time stir with a platinum stirring paddle. After the stirring paddle is pulled out, cool down to 1300-1500°C, keep warm for 2 hours and homogenize, and cast it on an iron mold to form For glass blocks with a size of about 80*160mm, preheat the mold to 450°C before casting the mold. After the glass block is hardened, immediately transfer it to an annealing furnace for annealing, keep it warm for 2 hours, then cool down to 140°C for 6 hours, cool naturally, and take it out for later use.

Step 2: Preparation of glass-ceramics

The above-mentioned glass preform is crystallized according to the following crystallization process, wherein TT1 refers to the time and temperature of the first crystallization process, and TT2 refers to the time and temperature of the second crystallization process:

TT1: 680℃, 6h;

TT2: 810°C, 1h;

The heating rate was 5°C/min.

Example 9

The present embodiment provides a glass-ceramic and a preparation method thereof, specifically as follows:

Step 1: Preparation of glass preforms

In terms of mass percentage, the following raw materials are mixed:

57% SiO ₂ , 23% Al ₂ O ₃ , 1.5% K ₂ O, 3.5% MgO, 4.5% Na ₂ O, 4% Li ₂ O, 4% ZrO ₂ , 0.5% B ₂ O ₃ , 1% P ₂ O ₅ , 1% ZnO;

After fully mixing evenly, use a platinum crucible to melt at 1500-1650°C for 8 hours, and at the same time stir with a platinum stirring paddle. After the stirring paddle is pulled out, cool down to 1300-1500°C, keep warm for 2 hours and homogenize, and cast it on an iron mold to form For glass blocks with a size of about 80*160mm, preheat to 450°C before casting the mold. After the glass blocks are hardened, immediately transfer them to an annealing furnace for annealing, keep them warm for 2 hours, then cool down to 140°C for 6 hours, cool naturally, and take them out for later use.

Step 2: Preparation of glass-ceramics

The above-mentioned glass preform is crystallized according to the following crystallization process, wherein TT1 refers to the time and temperature of the first crystallization process, and TT2 refers to the time and temperature of the second crystallization process:

TT1: 660°C, 4h;

TT2: 810°C, 0.5h;

The heating rate was 5°C/min.

Example 10

The present embodiment provides a glass-ceramic and a preparation method thereof, specifically as follows:

Step 1: Preparation of glass preforms

In terms of mass percentage, the following raw materials are mixed:

56% SiO ₂ , 26% Al ₂ O ₃ , 1.4% K ₂ O, 3.5% MgO, 5% Na ₂ O, 4.5% Li ₂ O, 3.6% ZrO ₂ ;

After fully mixing evenly, use a platinum crucible to melt at 1500-1650°C for 8 hours, and at the same time stir with a platinum stirring paddle. After the stirring paddle is pulled out, cool down to 1300-1500°C, keep warm for 2 hours and homogenize, and cast it on an iron mold to form For glass blocks with a size of about 80*160mm, preheat to 450°C before casting the mold. After the glass blocks are hardened, immediately transfer them to an annealing furnace for annealing, keep them warm for 2 hours, then cool down to 140°C for 6 hours, cool naturally, and take them out for later use.

Step 2: Preparation of glass-ceramics

The above-mentioned glass preform is crystallized according to the following crystallization process, wherein TT1 refers to the time and temperature of the first crystallization process, and TT2 refers to the time and temperature of the second crystallization process:

TT1: 650℃, 6h;

TT2: 790°C, 2h;

The heating rate is 2°C/min.

Example 11

The present embodiment provides a glass-ceramic and a preparation method thereof, specifically as follows:

Step 1: Preparation of glass preforms

In terms of mass percentage, the following raw materials are mixed:

56% SiO ₂ , 25% Al ₂ O ₃ , 1.5% K ₂ O, 1% MgO, 7% Na ₂ O, 5% Li ₂ O, 2% ZrO ₂ , 1% B ₂ O ₃ , 1.5% P ₂ O ₅ ;

After fully mixing evenly, use a platinum crucible to melt at 1500-1650°C for 8 hours, and at the same time stir with a platinum stirring paddle. After the stirring paddle is pulled out, cool down to 1300-1500°C, keep warm for 2 hours and homogenize, and cast it on an iron mold to form For glass blocks with a size of about 80*160mm, preheat to 450°C before casting the mold. After the glass blocks are hardened, immediately transfer them to an annealing furnace for annealing, keep them warm for 2 hours, then cool down to 140°C for 6 hours, cool naturally, and take them out for later use.

Step 2: Preparation of glass-ceramics

The above-mentioned glass preform is crystallized according to the following crystallization process, wherein TT1 refers to the time and temperature of the first crystallization process, and TT2 refers to the time and temperature of the second crystallization process:

TT1: 645°C, 4h;

TT2: 810°C, 1h;

The heating rate was 5°C/min.

Example 12

The present embodiment provides a glass-ceramic and a preparation method thereof, specifically as follows:

Step 1: Preparation of glass preforms

In terms of mass percentage, the following raw materials are mixed:

55% SiO ₂ , 25% Al ₂ O ₃ , 1% K ₂ O, 2% MgO, 4% Na ₂ O, 6.5% Li ₂ O, 1% ZrO ₂ , 3% B ₂ O ₃ , 0.5% P ₂ O ₅ , 2% ZnO;

After fully mixing evenly, use a platinum crucible to melt at 1500-1650°C for 8 hours, and at the same time stir with a platinum stirring paddle. After the stirring paddle is pulled out, cool down to 1300-1500°C, keep warm for 2 hours and homogenize, and cast it on an iron mold to form For glass blocks with a size of about 80*160mm, preheat to 450°C before casting the mold. After the glass blocks are hardened, immediately transfer them to an annealing furnace for annealing, keep them warm for 2 hours, then cool down to 140°C for 6 hours, cool naturally, and take them out for later use.

Step 2: Preparation of glass-ceramics

The above-mentioned glass preform is crystallized according to the following crystallization process, wherein TT1 refers to the time and temperature of the first crystallization process, and TT2 refers to the time and temperature of the second crystallization process:

TT1: 690°C, 4h;

TT2: 820°C, 1h;

The heating rate is 10°C/min.

Example 13

The present embodiment provides a glass-ceramic and a preparation method thereof, specifically as follows:

Step 1: Preparation of glass preforms

In terms of mass percentage, the following raw materials are mixed:

60.5% SiO ₂ , 24% Al ₂ O ₃ , 1% K ₂ O, 1.5% MgO, 4% Na ₂ O, 4.5% Li ₂ O, 1% ZrO ₂ , 3% B ₂ O ₃ , 0.5% P ₂ O ₅ ;

After fully mixing evenly, use a platinum crucible to melt at 1500-1650°C for 8 hours, and at the same time stir with a platinum stirring paddle. After the stirring paddle is pulled out, cool down to 1300-1500°C, keep warm for 2 hours and homogenize, and cast it on an iron mold to form For glass blocks with a size of about 80*160mm, preheat to 450°C before casting the mold. After the glass blocks are hardened, immediately transfer them to an annealing furnace for annealing, keep them warm for 2 hours, then cool down to 140°C for 6 hours, cool naturally, and take them out for later use.

Step 2: Preparation of glass-ceramics

The above-mentioned glass preform is crystallized according to the following crystallization process, wherein TT1 refers to the time and temperature of the first crystallization process, and TT2 refers to the time and temperature of the second crystallization process:

TT1: 700°C, 2h;

TT2: 820°C, 1h;

The heating rate was 5°C/min.

Example 14

The present embodiment provides a glass-ceramic and a preparation method thereof, specifically as follows:

Step 1: Preparation of glass preforms

In terms of mass percentage, the following raw materials are mixed:

63% SiO ₂ , 22% Al ₂ O ₃ , 1% K ₂ O, 1% MgO, 4.5% Na ₂ O, 5% Li ₂ O, 1% ZrO ₂ , 2% B ₂ O ₃ , 0.5% P ₂ O ₅ ;

After fully mixing evenly, use a platinum crucible to melt at 1500-1650°C for 8 hours, and at the same time stir with a platinum stirring paddle. After the stirring paddle is pulled out, cool down to 1300-1500°C, keep warm for 2 hours and homogenize, and cast it on an iron mold to form For glass blocks with a size of about 80*160mm, preheat to 450°C before casting the mold. After the glass blocks are hardened, immediately transfer them to an annealing furnace for annealing, keep them warm for 2 hours, then cool down to 140°C for 6 hours, cool naturally, and take them out for later use.

Step 2: Preparation of glass-ceramics

The above-mentioned glass preform is crystallized according to the following crystallization process, wherein TT1 refers to the time and temperature of the first crystallization process, and TT2 refers to the time and temperature of the second crystallization process:

TT1: 650℃, 4h;

TT2: 810°C, 1.5h;

The heating rate is 10°C/min.

Example 15

The present embodiment provides a glass-ceramic and a preparation method thereof, specifically as follows:

Step 1: Preparation of glass preforms

In terms of mass percentage, the following raw materials are mixed:

55% SiO ₂ , 25% Al ₂ O ₃ , 9% Na ₂ O, 3% Li ₂ O, 3% B ₂ O ₃ , 4% P ₂ O ₅ , 1% ZnO;

After fully mixing evenly, use a platinum crucible to melt at 1500-1650°C for 8 hours, and at the same time stir with a platinum stirring paddle. After the stirring paddle is pulled out, cool down to 1300-1500°C, keep warm for 2 hours and homogenize, and cast it on an iron mold to form For glass blocks with a size of about 80*160mm, preheat to 450°C before casting the mold. After the glass blocks are hardened, immediately transfer them to an annealing furnace for annealing, keep them warm for 2 hours, then cool down to 140°C for 6 hours, cool naturally, and take them out for later use.

Step 2: Preparation of glass-ceramics

The above-mentioned glass preform is crystallized according to the following crystallization process, wherein TT1 refers to the time and temperature of the first crystallization process, and TT2 refers to the time and temperature of the second crystallization process:

TT1: 650℃, 10h;

TT2: 820°C, 2h;

The heating rate is 2°C/min.

Example 16

The present embodiment provides a glass-ceramic and a preparation method thereof, specifically as follows:

Step 1: Preparation of glass preforms

In terms of mass percentage, the following raw materials are mixed:

53% SiO ₂ , 28% Al ₂ O ₃ , 1.5% MgO, 7% Na ₂ O, 3% Li ₂ O, 3.5% ZrO ₂ , 1% B ₂ O ₃ , 3% _{P2O5 ;}

After fully mixing evenly, use a platinum crucible to melt at 1500-1650°C for 8 hours, and at the same time stir with a platinum stirring paddle. After the stirring paddle is pulled out, cool down to 1300-1500°C, keep warm for 2 hours and homogenize, and cast it on an iron mold to form For glass blocks with a size of about 80*160mm, preheat to 450°C before casting the mold. After the glass blocks are hardened, immediately transfer them to an annealing furnace for annealing, keep them warm for 2 hours, then cool down to 140°C for 6 hours, cool naturally, and take them out for later use.

Step 2: Preparation of glass-ceramics

The above-mentioned glass preform is crystallized according to the following crystallization process, wherein TT1 refers to the time and temperature of the first crystallization process, and TT2 refers to the time and temperature of the second crystallization process:

TT1: 660℃, 6h;

TT2: 810°C, 4h;

The heating rate is 10°C/min.

Example 17

The present embodiment provides a glass-ceramic and a preparation method thereof, specifically as follows:

Step 1: Preparation of glass preforms

In terms of mass percentage, the following raw materials are mixed:

57% SiO ₂ , 25% Al ₂ O ₃ , 1.5% K ₂ O, 3.5% MgO, 4.5% Na ₂ O, 4% Li ₂ O, 3% ZrO ₂ , 0.5% B ₂ O ₃ , 1% ZnO;

After fully mixing evenly, use a platinum crucible to melt at 1500-1650°C for 8 hours, and at the same time stir with a platinum stirring paddle. After the stirring paddle is pulled out, cool down to 1300-1500°C, keep warm for 2 hours and homogenize, and cast it on an iron mold to form For glass blocks with a size of about 80*160mm, preheat to 450°C before casting the mold. After the glass blocks are hardened, immediately transfer them to an annealing furnace for annealing, keep them warm for 2 hours, then cool down to 140°C for 6 hours, cool naturally, and take them out for later use.

Step 2: Preparation of glass-ceramics

The above-mentioned glass preform is crystallized according to the following crystallization process, wherein TT1 refers to the time and temperature of the first crystallization process, and TT2 refers to the time and temperature of the second crystallization process:

TT1: 630℃, 8h;

TT2: 810°C, 1h;

The heating rate is 10°C/min.

Example 18

The present embodiment provides a glass-ceramic and a preparation method thereof, specifically as follows:

Step 1: Preparation of glass preforms

In terms of mass percentage, the following raw materials are mixed:

58.5% SiO ₂ , 25% Al ₂ O ₃ , 1.5% K ₂ O, 3.5% MgO, 4.5% Na ₂ O, 4% Li ₂ O, 2.5% ZrO ₂ , 0.5% B ₂ O ₃ ;

After fully mixing evenly, use a platinum crucible to melt at 1500-1650°C for 8 hours, and at the same time stir with a platinum stirring paddle. After the stirring paddle is pulled out, cool down to 1300-1500°C, keep warm for 2 hours and homogenize, and cast it on an iron mold to form For glass blocks with a size of about 80*160mm, preheat to 450°C before casting the mold. After the glass blocks are hardened, immediately transfer them to an annealing furnace for annealing, keep them warm for 2 hours, then cool down to 140°C for 6 hours, cool naturally, and take them out for later use.

Step 2: Preparation of glass-ceramics

The above-mentioned glass preform is crystallized according to the following crystallization process, wherein TT1 refers to the time and temperature of the first crystallization process, and TT2 refers to the time and temperature of the second crystallization process:

TT1: 645°C, 10h;

TT2: 780°C, 4h;

The heating rate was 5°C/min.

Example 19

The present embodiment provides a glass-ceramic and a preparation method thereof, specifically as follows:

Step 1: Preparation of glass preforms

In terms of mass percentage, the following raw materials are mixed:

61% SiO ₂ , 24% Al ₂ O ₃ , 1% K ₂ O, 1% MgO, 4% Na ₂ O, 5% Li ₂ O, 2% ZrO ₂ , 2% B ₂ O ₃ ;

After fully mixing evenly, use a platinum crucible to melt at 1500-1650°C for 8 hours, and at the same time stir with a platinum stirring paddle. After the stirring paddle is pulled out, cool down to 1300-1500°C, keep warm for 2 hours and homogenize, and cast it on an iron mold to form For glass blocks with a size of about 80*160mm, preheat the mold to 450°C before casting the mold. After the glass block is hardened, immediately transfer it to an annealing furnace for annealing, keep it warm for 2 hours, then cool down to 140°C for 6 hours, cool naturally, and take it out for later use.

Step 2: Preparation of glass-ceramics

The above-mentioned glass preform is crystallized according to the following crystallization process, wherein TT1 refers to the time and temperature of the first crystallization process, and TT2 refers to the time and temperature of the second crystallization process:

TT1: 645°C, 4h;

TT2: 810°C, 1h;

The heating rate is 2°C/min.

Example 20

The present embodiment provides a glass-ceramic and a preparation method thereof, specifically as follows:

Step 1: Preparation of glass preforms

In terms of mass percentage, the following raw materials are mixed:

62% SiO ₂ , 24% Al ₂ O ₃ , 0.5% K ₂ O, 0.5% MgO, 4.5% Na ₂ O, 5% Li ₂ O, 1% ZrO ₂ , 2% B ₂ O ₃ , 0.5% P ₂ O ₅ ;

After fully mixing evenly, use a platinum crucible to melt at 1500-1650°C for 8 hours, and at the same time stir with a platinum stirring paddle. After the stirring paddle is pulled out, cool down to 1300-1500°C, keep warm for 2 hours and homogenize, and cast it on an iron mold to form For glass blocks with a size of about 80*160mm, preheat the mold to 450°C before casting the mold. After the glass block is hardened, immediately transfer it to an annealing furnace for annealing, keep it warm for 2 hours, then cool down to 140°C for 6 hours, cool naturally, and take it out for later use.

Step 2: Preparation of glass-ceramics

The above-mentioned glass preform is crystallized according to the following crystallization process, wherein TT1 refers to the time and temperature of the first crystallization process, and TT2 refers to the time and temperature of the second crystallization process:

TT1: 690°C, 4h;

TT2: 820°C, 0.5h;

The heating rate is 10°C/min.

Example 21

The present embodiment provides a glass-ceramic and a preparation method thereof, specifically as follows:

Step 1: Preparation of glass preforms

In terms of mass percentage, the following raw materials are mixed:

62% SiO ₂ , 23% Al ₂ O ₃ , 0.5% K ₂ O, 0.5% MgO, 5% Na ₂ O, 5% Li ₂ O, 2% ZrO ₂ , 1.5% B ₂ O ₃ , 0.5% P ₂ O ₅ ;

After fully mixing evenly, use a platinum crucible to melt at 1500-1650°C for 8 hours, and at the same time stir with a platinum stirring paddle. After the stirring paddle is pulled out, cool down to 1300-1500°C, keep warm for 2 hours and homogenize, and cast it on an iron mold to form For glass blocks with a size of about 80*160mm, preheat the mold to 450°C before casting the mold. After the glass block is hardened, immediately transfer it to an annealing furnace for annealing, keep it warm for 2 hours, then cool down to 140°C for 6 hours, cool naturally, and take it out for later use.

Step 2: Preparation of glass-ceramics

The above-mentioned glass preform is crystallized according to the following crystallization process, wherein TT1 refers to the time and temperature of the first crystallization process, and TT2 refers to the time and temperature of the second crystallization process:

TT1: 645°C, 4h;

TT2: 810°C, 1h;

The heating rate is 2°C/min.

Example 22

The present embodiment provides a glass-ceramic and a preparation method thereof, specifically as follows:

Step 1: Preparation of glass preforms

In terms of mass percentage, the following raw materials are mixed:

62% SiO ₂ , 23% Al ₂ O ₃ , 1% K ₂ O, 0.5% MgO, 5% Na ₂ O, 5% Li ₂ O, 1.5% ZrO ₂ , 1.5% B ₂ O ₃ , 0.5% P ₂ O ₅ ;

After fully mixing evenly, use a platinum crucible to melt at 1500-1650°C for 8 hours, and at the same time stir with a platinum stirring paddle. After the stirring paddle is pulled out, cool down to 1300-1500°C, keep warm for 2 hours and homogenize, and cast it on an iron mold to form For glass blocks with a size of about 80*160mm, preheat to 450°C before casting the mold. After the glass blocks are hardened, immediately transfer them to an annealing furnace for annealing, keep them warm for 2 hours, then cool down to 140°C for 6 hours, cool naturally, and take them out for later use.

Step 2: Preparation of glass-ceramics

The above-mentioned glass preform is crystallized according to the following crystallization process, wherein TT1 refers to the time and temperature of the first crystallization process, and TT2 refers to the time and temperature of the second crystallization process:

TT1: 645°C, 4h;

TT2: 810°C, 1h;

The heating rate was 5°C/min.

Example 23

The present embodiment provides a glass-ceramic and a preparation method thereof, specifically as follows:

Step 1: Preparation of glass preforms

In terms of mass percentage, the following raw materials are mixed:

56% SiO ₂ , 23% Al ₂ O ₃ , 4% K ₂ O, 7% Na ₂ O, 3% Li ₂ O, 2% ZrO ₂ , 3% P ₂ O ₅ , 2 % ZnO;

After fully mixing evenly, use a platinum crucible to melt at 1500-1650°C for 8 hours, and at the same time stir with a platinum stirring paddle. After the stirring paddle is pulled out, cool down to 1300-1500°C, keep warm for 2 hours and homogenize, and cast it on an iron mold to form For glass blocks with a size of about 80*160mm, preheat to 450°C before casting the mold. After the glass blocks are hardened, immediately transfer them to an annealing furnace for annealing, keep them warm for 2 hours, then cool down to 140°C for 6 hours, cool naturally, and take them out for later use.

Step 2: Preparation of glass-ceramics

The above-mentioned glass preform is crystallized according to the following crystallization process, wherein TT1 refers to the time and temperature of the first crystallization process, and TT2 refers to the time and temperature of the second crystallization process:

TT1: 650℃, 10h;

TT2: 810°C, 1.5h;

The heating rate is 10°C/min.

Example 24

The present embodiment provides a glass-ceramic and a preparation method thereof, specifically as follows:

Step 1: Preparation of glass preforms

In terms of mass percentage, the following raw materials are mixed:

55% SiO ₂ , 25% Al ₂ O ₃ , 3% K ₂ O, 7% Na ₂ O, 4% Li ₂ O, 2% B ₂ O ₃ , 4% P ₂ O ₅ ;

After fully mixing evenly, use a platinum crucible to melt at 1500-1650°C for 8 hours, and at the same time stir with a platinum stirring paddle. After the stirring paddle is pulled out, cool down to 1300-1500°C, keep warm for 2 hours and homogenize, and cast it on an iron mold to form For glass blocks with a size of about 80*160mm, preheat to 450°C before casting the mold. After the glass blocks are hardened, immediately transfer them to an annealing furnace for annealing, keep them warm for 2 hours, then cool down to 140°C for 6 hours, cool naturally, and take them out for later use.

Step 2: Preparation of glass-ceramics

The above-mentioned glass preform is crystallized according to the following crystallization process, wherein TT1 refers to the time and temperature of the first crystallization process, and TT2 refers to the time and temperature of the second crystallization process:

TT1: 660℃, 10h;

TT2: 830°C, 1h;

The heating rate was 5°C/min.

Example 25

The present embodiment provides a glass-ceramic and a preparation method thereof, specifically as follows:

Step 1: Preparation of glass preforms

In terms of mass percentage, the following raw materials are mixed:

56% SiO ₂ , 25% Al ₂ O ₃ , 3% MgO, 7% Na ₂ O, 3% Li ₂ O, 3.5% ZrO ₂ , 1% B ₂ O ₃ , 1.5% _{P2O5 ;}

After fully mixing evenly, use a platinum crucible to melt at 1500-1650°C for 8 hours, and at the same time stir with a platinum stirring paddle. After the stirring paddle is pulled out, cool down to 1300-1500°C, keep warm for 2 hours and homogenize, and cast it on an iron mold to form For glass blocks with a size of about 80*160mm, preheat to 450°C before casting the mold. After the glass blocks are hardened, immediately transfer them to an annealing furnace for annealing, keep them warm for 2 hours, then cool down to 140°C for 6 hours, cool naturally, and take them out for later use.

Step 2: Preparation of glass-ceramics

The above-mentioned glass preform is crystallized according to the following crystallization process, wherein TT1 refers to the time and temperature of the first crystallization process, and TT2 refers to the time and temperature of the second crystallization process:

TT1: 700°C, 2h;

TT2: 820°C, 1h;

The heating rate is 10°C/min.

Effect verification test

The glass preforms obtained in step 1 of the above examples 1-25 were cut into 70*140*0.7mm glass sheets by STX-1203 wire cutting machine of Shenyang Kejing, and double-sided grinding by Shenzhen Haide HD-640-5L The polishing machine thins and polishes, and then grinds the edge by CNC, and uses the FALCON400 hardness tester from the Netherlands to test the surface Vickers hardness.

The glass-ceramics obtained in the above-mentioned embodiment 1-25 step 2 is tested for surface Vickers hardness by FALCON400 hardness tester of Netherland, and the transmittance of its 400-780nm wavelength range is tested by Lambda950 ultraviolet-visible spectrophotometer of PerkinElmer Company of the United States. Puset’s PT-307A universal testing machine tests the ring compressive strength (upper ring φ=16mm, lower ring φ=32mm), and Shenzhen Gaopin’s GP-2112-T directional drop tester tests the drop height of 180-grit sandpaper.

Cut the glass-ceramics obtained in step 2 of the above-mentioned Examples 1-25. After the cross-section is ground and polished, it is etched for 20 seconds with a 5 vol% HF solution. Phase layer thickness.

Cut the glass-ceramic obtained in step 2 of the above-mentioned Examples 1-25 into 20*20mm, test the crystal phase type of the composite glass-ceramic layer by Bruker’s X-ray diffractometer Bruker D8advance, and calculate its crystal phase type through its TOPAS software simulation. The proportions of different types of crystal phases and amorphous phases in the composite glass-ceramic layer.

The components, microcrystalline process parameters and effect experiment results of Examples 1-8 are shown in Table 1.

Table 1

The components, microcrystalline process parameters and effect experiment results of Examples 9-16 are shown in Table 2.

Table 2

The components, microcrystalline process parameters and effect experiment results of Examples 17-25 are shown in Table 3.

table 3

Wherein the XRD pattern of embodiment 1, embodiment 6 and embodiment 12 is respectively as shown in Figure 1, it can be seen that the β-spodumene (tetragonal crystal) in the crystal phase layer is less, especially less than below 10.4% , the transmittance of the 0.7mm sample is higher than 90%, and it is transparent; β-spodumene (tetragonal crystal) is gradually increasing, especially higher than 40%, and the transmittance of the 0.7mm sample is lower than 72%, and it is opaque White exterior.

Figure 2 is a typical cross-sectional scanning electron microscope image of the sample in Example 12. It can be seen that after the above-mentioned glass composition is subjected to an appropriate crystallization process, a layer of crystal phase layer with a thickness of 2 μm to 90 μm can be uniformly precipitated on the surface layer, which is in common with the middle glass layer. A glass-ceramic composition with surface crystallization is combined to form a uniform and dense compressive stress layer on the glass surface through the volume change caused by surface crystallization, which can significantly improve the surface hardness and sandpaper drop resistance of the glass.

The technical features of the above-mentioned embodiments can be combined arbitrarily. To make the description concise, all possible combinations of the technical features in the above-mentioned embodiments are not described. However, as long as there is no contradiction in the combination of these technical features, should be considered as within the scope of this specification.

The above-mentioned embodiments only express several implementation modes of the present invention, which are convenient for a specific and detailed understanding of the technical solution of the present invention, but should not be construed as limiting the protection scope of the invention patent. It should be noted that those skilled in the art can make several modifications and improvements without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. It should be understood that technical solutions obtained by those skilled in the art through logical analysis, reasoning or limited experiments on the basis of the technical solutions provided by the present invention are within the protection scope of the appended claims of the present invention. Therefore, the protection scope of the patent for the present invention shall be determined by the content of the appended claims, and the description and drawings may be used to interpret the content of the claims.

Claims (11)

1. A glass-ceramic, characterized in that the glass-ceramic comprises a glass substrate and a composite glass-ceramic layer coated on the surface of the glass substrate;

   Wherein, the composite glass-ceramics layer includes hexagonal β-spodumene, tetragonal β-spodumene and other glasses.
2. The glass-ceramic according to claim 1, characterized in that, in terms of mass percentage, the composite glass-ceramic layer comprises 19.2% to 88.5% of the hexagonal β-spodumene, 3% to 75.8% % of the tetragonal β-spodumene and 5% to 14.8% of the other glasses.
3. The glass-ceramic according to claim 1, wherein the other glasses include SiO ₂ , Al ₂ O ₃ , Li ₂ O, Na ₂ O and other oxides; the other oxides are selected from K ₂ O , MgO, ZrO ₂ , B ₂ O ₃ , P ₂ O ₅ and ZnO at least three; and/or

   The glass matrix includes SiO ₂ , Al ₂ O ₃ , Li ₂ O, Na ₂ O and other oxides; the other oxides are selected from K ₂ O, MgO, ZrO ₂ , B ₂ O ₃ , P ₂ O ₅ with at least three of ZnO.
4. The glass-ceramic according to claim 1, characterized in that the thickness of the composite glass-ceramic layer is 2 μm˜90 μm.
5. A method for preparing glass-ceramics according to any one of claims 1 to 4, characterized in that it comprises the steps of:

   Preparing a glass preform, subjecting the glass preform to first crystallization and second crystallization to prepare the composite glass-ceramic layer;

   Among them, the temperature for the first crystallization is 630°C-700°C, and the time for the first crystallization is 2h-10h;

   After the first crystallization is completed, the temperature is raised to carry out the second crystallization, the temperature of the second crystallization is 780°C-830°C, and the time of the second crystallization is 0.5h-4h.
6. The method for preparing glass-ceramic according to claim 5, characterized in that preparing the glass preform comprises the following steps: mixing the raw materials of the glass preform, melting at 1500°C-1650°C for 7h-9h, and then Cool down to 1300°C-1500°C, keep warm for 1.5h-2.5h, shape, prepare glass block, anneal after the glass block is hardened, and cool down;

   Wherein, the raw material of the glass preform includes SiO ₂ , Al ₂ O ₃ , Li ₂ O, Na ₂ O and other oxides; the other oxides are selected from K ₂ O, MgO, ZrO ₂ , B ₂ O ₃ , P ₂ O ₅ and ZnO at least three.
7. The method for preparing glass ceramics according to claim 6, characterized in that, in terms of mass percentage, the raw materials of the glass preform include 50% to 68% SiO ₂ , 18% to 29.5% Al ₂ O ₃ , 2 %-6.5% Li ₂ O, 3%-10% Na ₂ O and 0.1%-15% of other oxides.
8. The method for preparing glass-ceramic according to any one of claims 5-7, characterized in that the temperature for the first crystallization is 660°C-700°C, and the time for the first crystallization is 2h-10h.
9. The method for preparing glass-ceramic according to any one of claims 5-7, characterized in that the temperature of the second crystallization is 810°C-830°C, and the time of the second crystallization is 1h-4h.
10. The method for preparing glass-ceramic according to any one of claims 5-7, characterized in that the heating rate is 2°C/min-10°C/min.
11. Application of the glass-ceramic according to any one of claims 1 to 4 in protective glass, special glass and architectural glass of electronic devices.

Images