WO2024055374A1

WO2024055374A1 - Tempered glass, glass-ceramic, and preparation method therefor and use thereof

Info

Publication number: WO2024055374A1
Application number: PCT/CN2022/124239
Authority: WO
Inventors: 平文亮; 蒋江; 刘红刚; 王明忠; 肖子凡; 王琰; 康庆伟; 赵北玉
Original assignee: 清远南玻节能新材料有限公司; 咸宁南玻光电玻璃有限公司; 中国南玻集团股份有限公司
Priority date: 2022-09-14
Filing date: 2022-10-10
Publication date: 2024-03-21
Also published as: CN117700111A

Abstract

A tempered glass, a glass-ceramic, and a preparation method therefor and a use thereof. The glass-ceramic comprises the following components in percentage by mass: 54-66% of SiO₂, 17-28% of Al₂O₃, 0.5-4% of MgO, 2-8% of Na₂O, 2-6.5% of Li₂O, 0.5-2% of P₂O₅, and 1-5% of TiO₂, wherein the crystalline phase of the glass-ceramic comprises β-spodumene.

Description

Strengthened glass, glass-ceramics and their preparation methods and applications

Related applications

This application claims priority to the Chinese patent application filed on September 14, 2022, with application number 2022111160899 and titled "Strengthened Glass, Crystallized Glass and Preparation Methods and Applications thereof", the full text of which is hereby incorporated by reference.

Technical field

The present application relates to the technical field of glass products, specifically to a kind of strengthened glass, glass-ceramics and their preparation methods and applications.

Background technique

Crystallized glass, also known as glass-ceramics, generally refers to basic glass with a specific composition. A large number of crystals are washed out under a heat treatment process to form a multi-phase complex of crystalline and glass phases. It has the excellent properties of both glass and ceramics. Crystallized glass has the advantages of high mechanical strength and excellent insulation properties, and is especially suitable for use as protective glass for consumer electronics.

However, in order to further obtain higher mechanical strength, traditional technology also usually chemically strengthens the glass-ceramics. Chemically strengthened glass-ceramics have high compressive stress, but poor fracture toughness, resulting in poor drop resistance, and are prone to breakage and produce a large number of small fragments, making them less safe to use.

Contents of the invention

Based on the above problems, this application provides a strengthened glass, crystallized glass and their preparation methods and applications.

In one aspect of the application, a crystallized glass is provided, the components of which include, in terms of mass percentage:

Wherein, the crystal phase of the crystallized glass includes β-spodumene.

In any embodiment, the crystallized glass has a crystallinity of ≥55%.

In any embodiment, the mass content of β-spodumene in the crystallized glass is 23% to 90%.

In any embodiment, the crystalline phase of the glass-ceramic further includes eucryptite.

In any embodiment, the mass content of the eucryptite in the crystallized glass is ≤32%.

In any embodiment, the crystallized glass satisfies at least one of the conditions (1) to (11):

(1) The mass content of SiO ₂ is 54% to 63%;

(2) The mass content of Al ₂ O ₃ is 18% to 27%;

(3) The mass content of K ₂ O is 0 to 1.5%;

(4) The mass content of MgO is 0.5% to 3.5%;

(5) The mass content of Na ₂ O is 3.5% to 6%;

(6) The mass content of Li ₂ O is 3% to 6.5%;

(7) The mass content of ZrO ₂ is 1% to 4%;

(8) The mass content of B ₂ O ₃ is 0 to 3%;

(9) The mass content of P ₂ O ₅ is 0.5% to 1%;

(10) The mass content of ZnO is 0 to 1%;

(11) The mass content of TiO ₂ is 1% to 4%.

In a second aspect, this application also provides a method for preparing the crystallized glass of the first aspect, including the following steps:

Prepare raw materials according to the components of the crystallized glass;

Melt the raw materials into clear glass liquid;

Shape the clarified glass liquid to prepare precursor glass;

The precursor glass is sequentially subjected to nucleation treatment and crystallization treatment to prepare the crystallized glass.

In any embodiment, the temperature of the nucleation treatment is 630°C to 700°C; the time of the nucleation treatment is 2h to 10h;

The temperature of the crystallization treatment is 780°C to 830°C; the time of the crystallization treatment is 0.5h to 4h.

In a third aspect, the present application also provides a strengthened glass, which is obtained by chemically strengthening the crystallized glass of the first aspect.

In any embodiment, the surface stress value of the strengthened glass is ≥645MPa, and the deep stress depth Dol-Na is ≥138 μm.

In any embodiment, the tempered glass satisfies at least one of the conditions (i) to (iii):

(i) The surface Vickers hardness of the strengthened glass is ≥730Hv;

(ii) The ring crushing strength of the strengthened glass is ≥650N;

(iii) The drop height of 180-grit sandpaper for the tempered glass is ≥1.5m.

In a fourth aspect, this application also provides a method for preparing the tempered glass of the third aspect, which includes the following steps:

The crystallized glass is subjected to a first strengthening treatment in a first molten salt; in terms of mass percentage, the first molten salt includes 40% to 60% sodium nitrate and 40% to 60% potassium nitrate;

The crystallized glass that has undergone the first strengthening treatment is subjected to a second strengthening treatment in a second molten salt; in terms of mass percentage, the second molten salt includes 0 to 4% sodium nitrate and 96% to 100 % potassium nitrate.

In any embodiment, the temperature of the first strengthening treatment is 440°C to 500°C; the time of the first strengthening treatment is 4h to 16h;

The temperature of the second strengthening treatment is 380°C to 420°C; the time of the second strengthening treatment is 1h to 4h.

In a fifth aspect, this application also provides the application of the tempered glass of the third aspect in preparing electronic products.

In a sixth aspect, the present application provides an electronic product, including a body and a protective glass embedded in the body, where the protective glass is the tempered glass of the third aspect.

The components of the above-mentioned glass-ceramics include specific contents of SiO ₂ , Al ₂ O ₃ , MgO, Li ₂ O, Na ₂ O, P ₂ O ₅ and TiO ₂ etc., and the crystal phase of the glass-ceramics includes β-spodumene. . Through reasonable component proportions, the above-mentioned glass-ceramics, after chemical strengthening, have both high compressive stress and good crack expansion resistance, as well as high surface Vickers hardness and high ring pressure strength; Therefore, it has good impact resistance and is not easily broken into small glass fragments after impact, making it safer to use.

Description of drawings

In order to more clearly explain the technical solutions in the embodiments of the present application or the traditional technology, the drawings needed to be used in the description of the embodiments or the traditional technology will be briefly introduced below. Obviously, the drawings in the following description are only for the purpose of explaining the embodiments or the technical solutions of the traditional technology. For the embodiments of the application, those of ordinary skill in the art can also obtain other drawings based on the disclosed drawings without exerting creative efforts.

Figure 1 is a flow chart of a method for preparing crystallized glass according to an embodiment of the present application;

Figure 2 is a flow chart of a preparation method of tempered glass according to an embodiment of the present application;

Figure 3 is an X-ray diffraction pattern (XRD) of the crystallized glass of Example 19 of the present application;

Figure 4 is an appearance view of the tempered glass in Example 1 of the present application after passing the ball drop test;

Figure 5 is an appearance view of the tempered glass in Comparative Example 1 of the present application after passing the ball drop test.

Detailed ways

The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present application. Obviously, the described embodiments are only some of the embodiments of the present application, rather than all of the embodiments. Based on the embodiments in this application, all other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the scope of protection of this application.

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 to which this application belongs. The terminology used herein in the description of the application is for the purpose of describing specific embodiments only and is not intended to limit the application. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.

One embodiment of the present application provides a crystallized glass, the components of which include, in terms of mass percentage:

Among them, the crystal phase of glass-ceramics includes β-spodumene.

The components of the above-mentioned glass-ceramics include specific contents of SiO ₂ , Al ₂ O ₃ , MgO, Li ₂ O, Na ₂ O, P ₂ O ₅ and TiO ₂ etc., and the crystal phase of the glass-ceramics includes β-spodumene. . The chemical composition of β-spodumene is LiAl(SiO ₃ ) _2. It belongs to the tetragonal crystal system and has thermal cracking properties, which can improve the mechanical strength and thermal shock resistance of glass-ceramics. Through reasonable component proportions, the above-mentioned glass-ceramics, after chemical strengthening, have both high compressive stress and good crack expansion resistance, as well as high surface Vickers hardness and high ring pressure strength; Therefore, it has good impact resistance and is not easily broken into small glass fragments after impact, making it safer to use.

In addition, compared with the traditional glass-ceramics of the lithium disilicate system, the above-mentioned glass-ceramics have a lower content of Li ₂ O, which can significantly reduce the production cost of the glass-ceramics.

In some embodiments, the crystallized glass has a crystallinity of ≥55%. The crystallinity of glass-ceramics is within the above range, and the glass-ceramics has good mechanical properties. Optionally, the crystallization degree of the crystallized glass is ≥55%, ≥60%, ≥65%, ≥70%, ≥75%, ≥80%, ≥85% or ≥90%. In some embodiments, the crystallization degree of the crystallized glass is 55% to 93%, 72.3% to 88.5%, or 80% to 90%.

The β-spodumene crystal phase has properties such as low expansion and high mechanical strength, which can improve the mechanical strength and heat resistance of glass-ceramics. In some embodiments, the mass content of β-spodumene in the glass-ceramic is 23% to 90%. Optionally, the mass content of β-spodumene in the glass-ceramics is in the range of any of the following values: 23%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60% , 65%, 70%, 75%, 80%, 85% or 90%. Further, the mass content of β-spodumene in the crystallized glass is 23% to 81%, 43.2% to 88.5%, or 52% to 90%.

In some embodiments, the crystalline phase of the glass-ceramics further includes eucryptite. The chemical composition of eucryptite, LiAlSiO ₄ , has a low expansion coefficient, high strength, hardness and wear resistance, and can improve the mechanical strength of glass-ceramics. In some embodiments, the mass content of eucryptite in the glass-ceramic is ≤32%. Optionally, the mass content of eucryptite in the crystallized glass is in the range of any of the following values: 0, 5%, 10%, 15%, 20%, 25%, 30% or 32%. Further, the mass content of eucryptite in the crystallized glass is 0% to 30%, 0% to 30.7%, or 7% to 32%.

In some embodiments, the mass content of the glass phase in the crystallized glass is ≤ 45%. Optionally, the mass content of the glass phase in the crystallized glass is in the range of any of the following values: 7%, 10%, 15%, 20%, 25%, 30%, 35%, 40% or 45%. Further, the mass content of the glass phase in the crystallized glass is 7% to 45%, 11.5% to 27.7%, or 10% to 20%.

In some embodiments, the average transmittance of the crystallized glass in the range of 400 nm to 780 nm is ≥49.8%. Optionally, the average transmittance of the crystallized glass from 400nm to 780nm is in the range of any of the following values: 49.8%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90% Or 91.8%.

_SiO2 is an oxide involved in glass forming and can be used to stabilize glass and glass-ceramic network structures. In the embodiment of the present application, the mass content of SiO ₂ in the crystallized glass is 54% to 66%. Optionally, the mass content of SiO ₂ in the crystallized glass is in the range of any of the following values: 54%, 55%, 56%, 58%, 60%, 62%, 63%, 65% or 66%. Further, the mass content of SiO ₂ in the crystallized glass is 54% to 63% or 56% to 65%.

Al ₂ O ₃ also stabilizes the network and also provides improved mechanical properties and chemical durability. In the embodiment of the present application, the mass content of Al ₂ O ₃ in the crystallized glass is 17% to 28%. Optionally, the mass content of Al ₂ O ₃ in the crystallized glass is in the range of any of the following values: 17%, 18%, 20%, 22%, 24%, 25%, 26%, 27% or 28%. Further, the mass content of Al ₂ O ₃ in the crystallized glass is 18% to 27%.

Li ₂ O is one of the components that form the β-spodumene crystal phase, and also serves as a co-solvent and a component that enhances ion exchange capabilities. In the embodiment of the present application, the mass content of Li ₂ O in the crystallized glass is 2% to 6.5%. Optionally, the mass content of Li ₂ O in the crystallized glass is in the range of any of the following values: 2%, 3%, 4%, 5%, 6% or 6.5%. Further, the mass content of Li ₂ O in the crystallized glass is 2% to 6%, 3% to 6.5%, or 2% to 5%.

The role of Na ₂ O is similar to that of Li ₂ O. It serves as a co-solvent and a component that enhances ion exchange capabilities in glass-ceramics. However, too much Na ₂ O will cause too many glass phases in the glass-ceramics, affecting glass products. mechanical strength. In the embodiment of the present application, the mass content of Na ₂ O in the crystallized glass is 2% to 8%. Optionally, the mass content of Na ₂ O in the crystallized glass is in the range of any of the following values: 2%, 3%, 4%, 5%, 6%, 7% or 8%. Further, the mass content of Na ₂ O in the crystallized glass is 3.5% to 6% or 4% to 6%.

The role of K ₂ O is similar to that of Na ₂ O, which will also lead to too much glass phase remaining, and too much K ₂ O is not conducive to the chemical strengthening properties of the glass-ceramics and will reduce the power of Na-K ion exchange. In the embodiment of the present application, the mass content of K ₂ O in the crystallized glass is 0 to 2%. Optionally, the mass content of K ₂ O in the crystallized glass is in the range of any of the following values: 0, 0.5%, 1%, 1.5% or 2%. Further, the mass content of K ₂ O in the crystallized glass is 0 to 1.5%.

MgO is beneficial to reducing the high-temperature viscosity of the base glass, modifying the glass structure, and improving the strength and chemical stability of the base glass. In the embodiment of the present application, the mass content of MgO in the crystallized glass is 0.5% to 4%. Optionally, the mass content of MgO in the crystallized glass is in the range of any of the following values: 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5% or 4%. Further, the mass content of MgO in the crystallized glass is 0.5% to 3.5%.

The role of ZnO is similar to that of MgO, which is beneficial to reducing the high-temperature viscosity of the base glass, modifying the glass structure, and improving the strength and chemical stability of the base glass. In the embodiment of the present application, the mass content of ZnO in the crystallized glass is 0 to 3%. Optionally, the mass content of ZnO in the crystallized glass is in the range of any of the following values: 0, 0.5%, 1%, 1.5%, 2%, 2.5% or 3%. Further, the mass content of ZnO in the crystallized glass is 0 to 1%.

_ZrO2 is added as a commonly used nucleating agent. ZrO ₂ can improve the stability of the Li ₂ O-Al ₂ O ₃ -SiO ₂ glass system by significantly reducing the glass devitrification during the formation process and lowering the liquidus temperature. In the embodiment of the present application, the mass content of ZrO ₂ in the crystallized glass is 0 to 4%. Optionally, the mass content of ZrO ₂ in the crystallized glass is in the range of any of the following values: 0, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5% or 4%. Further, the mass content of ZrO ₂ in the crystallized glass is 1% to 4%.

TiO ₂ has a similar effect to ZrO ₂ and can form fine crystal nuclei in the glass, but too much will cause the base glass to turn yellow. In the embodiment of the present application, the mass content of TiO ₂ in the crystallized glass is 1% to 5%. Optionally, the mass content of TiO ₂ in the crystallized glass is in the range of any of the following values: 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5% or 5%. Further, the mass content of TiO ₂ in the crystallized glass is 1% to 4%.

P ₂ O ₅ can be used as a nucleating agent to promote glass nucleation. In the embodiment of the present application, the mass content of P ₂ O ₅ in the crystallized glass is 0.5% to 2%. Optionally, the mass content of P ₂ O ₅ in the glass-ceramics is in the range of any of the following values: 0.5%, 0.6%, 0.8%, 1%, 1.2%, 1.4%, 1.5%, 1.6%, 1.8% or 2%. Further, the mass content of P ₂ O ₅ in the crystallized glass is 0.5% to 1%.

B ₂ O ₃ helps provide a base glass with a low melting temperature. In addition, adding B ₂ O ₃ to the base glass promotes phase separation, nucleation and crystallization of the base glass and shortens the crystallization time of the base glass. In the embodiment of the present application, the mass content of B ₂ O ₃ in the crystallized glass is 0 to 5%. Optionally, the mass content of B ₂ O ₃ in the crystallized glass is in the range of any of the following values: 0, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5 % or 5%. Further, the mass content of B ₂ O ₃ in the crystallized glass is 0 to 3%.

In some embodiments, the components of the glass-ceramics in terms of mass percentage include: SiO ₂ 54% to 66%, Al ₂ O ₃ 17% to 28%, K ₂ O 0 to 2%, MgO 0.5% to 4 %, Na ₂ O 2% to 8%, Li ₂ O 2% to 6.5%, ZrO ₂ 0 to 0.5%, B ₂ O ₃ 0 to 5%, P ₂ O ₅ 0.5% to 2%, ZnO 0 to 3 %, and TiO ₂ 1% ~ 5%; among them, the phase composition of glass-ceramics in terms of mass percentage includes: 43.2% ~ 88.5% β-spodumene crystal phase, 0 ~ 30.7% eucryptite crystal phase And 11.5% to 27.7% glass phase.

In some embodiments, the components of the crystallized glass include, in terms of mass percentage: SiO ₂ 54% to 63%, Al ₂ O ₃ 18% to 27%, K ₂ O 0 to 1.5%, MgO 0.5% to 3.5 %, Na ₂ O 4% ~ 6%, Li ₂ O 3% ~ 6.5%, ZrO ₂ 1% ~ 1.5%, B ₂ O ₃ 0 ~ 3%, P ₂ O ₅ 0.5% ~ 2%, ZnO 0 ~ 1% and TiO ₂ 3% to 4%; among them, the phase composition of glass-ceramics in terms of mass percentage includes: 23% to 81% β-spodumene crystal phase, 7% to 32% eucryptite crystal Phase and 7% to 45% glass phase.

In some embodiments, the components of the crystallized glass include, in terms of mass percentage: SiO ₂ 56% to 65%, Al ₂ O ₃ 20% to 25%, K ₂ O 0 to 1.5%, MgO 0.5% to 3.5 %, Na ₂ O 3.5% ~ 6%, Li ₂ O 2% ~ 5%, ZrO ₂ 2% ~ 4%, B ₂ O ₃ 0 ~ 2%, P ₂ O ₅ 0.5% ~ 1%, ZnO 0 ~ 1% and TiO ₂ 1% ~ 3.5%; among them, the phase composition of glass-ceramics in terms of mass percentage includes: 52% ~ 90% β-spodumene crystal phase, 0 ~ 30% eucryptite crystal phase And 10% to 20% glass phase.

Referring to Figure 1, another embodiment of the present application also provides a method for preparing crystallized glass, including the following steps S110 to S140 to prepare the crystallized glass of the first aspect:

Step S110: Prepare raw materials according to the components of the crystallized glass.

Step S120: Melt raw materials into clear glass liquid.

In some embodiments, in step S120, the melting temperature is 1500°C to 1650°C. The melting time is 4h~10h.

Step S130: Shape the clear glass liquid to prepare precursor glass.

In some embodiments, in step S130, the forming process is selected from one of the float forming process, the overflow down-drawing method, the upward drawing method, the flat drawing method and the rolling method.

Step S140: Perform nucleation treatment and crystallization treatment on the precursor glass in sequence to prepare crystallized glass.

In some embodiments, in step S140, the temperature of the nucleation treatment is 630°C to 700°C; the time of the nucleation treatment is 2h to 10h.

In some embodiments, in step S140, the temperature of the crystallization treatment is 780°C to 830°C; the time of the crystallization treatment is 0.5h to 4h.

Another embodiment of the present application also provides a strengthened glass, which is obtained by chemically strengthening the crystallized glass of the first aspect.

The protective glass of smart electronic equipment falls and breaks, causing failure. The degree of breakage of glass needs to be controlled in the industry. Many glasses can often obtain higher mechanical strength through chemical strengthening. However, due to excessive internal stress, they are in a shattered state after breakage and become fragments. The average size is less than 2mm. On the one hand, too many cracks hinder the continued use of smart devices such as mobile phones. The cracks have blocked the screen; on the other hand, too fine broken glass is easy to fall off and has the risk of entering the eyes of consumers or children. Risk of ingestion, etc.

The inventor found through research that the above-mentioned tempered glass is obtained by chemically strengthening the crystal glass with the above-mentioned specific composition ratio. Strengthened glass has both high surface stress and good crack propagation resistance. Strengthened glass has better drop resistance and scratch resistance on rough surfaces. The average size of the fragments after the tempered glass is broken is larger, the fragments are not easy to fall off, and the use safety is better.

In some embodiments, the surface stress value of the strengthened glass is ≥645MPa, and the deep stress depth Dol-Na is ≥138 μm. In some embodiments, the surface stress value of the strengthened glass is 645MPa˜1045MPa, 745MPa˜904MPa, 867MPa˜984MPa, or 979MPa˜1045MPa. The deep stress depth Dol-Na is 138 μm to 159 μm, 138 μm to 154 μm, 139 μm to 159 μm, or 143 μm to 157 μm.

In some of these embodiments, the strengthened glass has a surface Vickers hardness ≥730 Hv. In some embodiments, the strengthened glass has a surface Vickers hardness of 730Hv˜822Hv, 734Hv˜766Hv, 734Hv˜779Hv, or 773Hv˜822Hv.

In some of the embodiments, the strengthened glass has a ring crush strength ≥650N. In some embodiments, the ring crush strength of the strengthened glass is 650N～903N, 668N～893N, 662N～903N or 653N～892N.

In some of these embodiments, the tempered glass has a drop height of 180 grit sandpaper ≥1.5m. In some embodiments, the 180-grit sandpaper drop height of the strengthened glass is 1.7 m to 1.9 m, 1.7 m to 2.0 m, or 1.8 m to 2.0 m.

Referring to Figure 2, another embodiment of the present application also provides a method for preparing the tempered glass of the third aspect, including the following steps S210 and S220:

Step S210: Perform the first strengthening treatment on the crystallized glass in the first molten salt; in terms of mass percentage, the first molten salt includes 40% to 60% sodium nitrate and 40% to 60% potassium nitrate.

In some embodiments, in step S210, the temperature of the first strengthening treatment is 440°C to 500°C; the time of the first strengthening treatment is 4h to 16h.

Step S220: Perform a second strengthening treatment on the first strengthened glass-ceramics in a second molten salt; in terms of mass percentage, the second molten salt includes 0-4% sodium nitrate and 96%-100% nitric acid. Potassium.

In some embodiments, the temperature of the second strengthening treatment in step S220 is 380°C to 420°C; the time of the second strengthening treatment is 1h to 4h.

Another embodiment of the present application also provides the application of the above-mentioned third aspect of the tempered glass in the preparation of electronic products.

Another embodiment of the present application also provides an electronic product, including a body and a protective glass embedded in the body, where the protective glass is the tempered glass of the third aspect.

The strengthened glass, crystallized glass and preparation method of the present application will be further described below through specific examples.

Embodiments 1 to 24 and Comparative Examples 1 to 8 were distributed according to the designed components (mass percentage) in Tables 1 to 4. After being thoroughly mixed, they were melted in a platinum crucible at 1500°C to 1650°C for 8 hours. Stir with the stirring paddle. After pulling out the stirring paddle, cool down to 1300℃~1500℃, keep the temperature for 2 hours and homogenize. Cast it on the iron mold to form a glass block of about 80mm*160mm. Preheat the mold to 450℃ before casting. The glass block After hardening, immediately transfer to the annealing furnace for annealing, keep warm for 2 hours, then lower the temperature to 140°C for 6 hours, cool naturally, and take it out for later use.

The glass samples of Examples 1 to 24 and Comparative Examples 1 to 8 were cut into 70*140*0.7mm glass sheets by Shenyang Kejing's STX-1203 wire cutting machine, and double-sided polished by Shenzhen Haide's HD-640-5L The polishing machine is used to thin and polish, and then CNC grinding is performed, and the surface Vickers hardness is tested using the FALCON400 hardness tester from Inno of the Netherlands.

The samples of the above-mentioned Examples 1 to 24 and Comparative Examples 1 to 8 were processed according to the nucleation and crystallization processes shown in Tables 1 to 4. The crystallized samples were cut, and the cross sections were ground and polished before use. The above sample was cut into 20*20mm, and its crystalline phase types were tested through Bruker's X-ray diffractometer Bruker D8 advance, and its different types of crystalline phase proportions and amorphous phase proportions were simulated and calculated through its TOPAS software, which are recorded in Table 1 ~Table 4.

The above-mentioned crystallized sample is processed through a secondary strengthening process. The first chemical strengthening is to soak in a mixed solution of 40wt% to 60wt% sodium nitrate and 60wt% to 40wt% potassium nitrate at 440°C to 500°C for 4h- 16h; the second chemical strengthening is a mixed solution of 96wt%~100wt% potassium nitrate and 4wt%-0wt% sodium nitrate, soaked at 380℃~420℃ for 1h-4h; passed the surface stress of Japan Orihara Industrial Co., Ltd. SLP2000 and FSM-6000LE The Na-K surface compressive stress CS (Mpa) and the Li-Na exchange stress depth Dol_0 (μm) were tested using a tester. The FALCON400 hardness tester from the Netherlands was used to test the surface Vickers hardness. The Lambda950 UV-visible spectrophotometer from the American PerkinElmer company was used to test the surface. Its transmittance in the wavelength range of 400nm ~ 780nm, Puset's PT-307A universal testing machine tested the ring pressure strength (upper ring φ = 16mm, lower ring φ = 32mm), Shenzhen Gaopin's GP-2112-T directional drop The tester tests the drop height of 180-grit sandpaper and observes the morphology of glass cracks, which are recorded in Tables 1 to 4. Depending on the degree of shattering, glass cracks are divided into two levels: shattering and cracking. The average shattered fragment size is less than 5mm or the intact glass area is less than 1/3, which is often unacceptable; and when it is determined to be cracked, the average shattered If the crack size is >5mm and more than 1/3 of the glass area is present, it is intact.

Table 1

The glass components of Examples 1 to 8 include, in terms of mass percentage: SiO ₂ 54% to 66%, Al ₂ O ₃ 17% to 28%, K ₂ O 0 to 2%, MgO 0.5% to 4%, Na ₂ O 2% ~ 8%, Li ₂ O 2% ~ 6.5%, ZrO ₂ 0 ~ 0.5%, B ₂ O ₃ 0 ~ 5%, P ₂ O ₅ 0.5% ~ 2%, ZnO 0 ~ 3%, And TiO ₂ 1% ~ 5%. The surface Vickers hardness of the precursor glass is 578Hv to 628Hv. After nucleation and crystallization treatment, the phase composition of glass-ceramics in terms of mass percentage includes: 43.2% ~ 88.5% β-spodumene crystal phase, 0 ~ 30.7% eucryptite crystal phase and 11.5% ~ 27.7% glass phase; the appearance of crystallized glass is transparent or translucent, and the average transmittance from 400 to 780nm is 62.9% to 91.2%. After two-step chemical strengthening treatment, the surface stress value of the glass (K-Na compressive stress CS) is 745MPa ~ 904MPa, and the deep stress depth (Li-Na exchange stress depth Dol-Na) is 138.4μm ~ 153.6μm. The surface Vickers hardness of the strengthened glass-ceramic is ≥734Hv, the 180-mesh surface ball drop height is ≥1.7m, the ring pressure strength is ≥668MPa, and the broken appearance is cracked.

Table 2

The glass components of Examples 9 to 16 include, in terms of mass percentage: SiO ₂ 54% to 63%, Al ₂ O ₃ 18% to 27%, K ₂ O 0 to 1.5%, MgO 0.5% to 3.5%, Na ₂ O 4% ~ 6%, Li ₂ O 3% ~ 6.5%, ZrO ₂ 1% ~ 1.5%, B ₂ O ₃ 0 ~ 3%, P ₂ O ₅ 0.5% ~ 2%, ZnO 0 ~ 1% , and TiO ₂ 3% to 4%. The surface Vickers hardness of the precursor glass is 584Hv to 630Hv. After nucleation and crystallization treatment, the phase composition of glass-ceramics in terms of mass percentage includes: 23% to 81% β-spodumene crystal phase, 7% to 32% eucryptite crystal phase and 7% ~45% glass phase; the appearance of crystallized glass is transparent or translucent, and the average transmittance from 400 to 780nm is 49.8% to 91.4%. After two-step chemical strengthening treatment, the surface stress value of the glass (K-Na compressive stress CS) is 867MPa ~ 984MPa, and the deep stress depth (Li-Na exchange stress depth Dol-Na) is 139.5μm ~ 158.4μm. The surface Vickers hardness of the strengthened glass-ceramic is ≥739Hv, the 180-mesh surface ball drop height is ≥1.7m, the ring pressure strength is ≥662MPa, and the broken appearance is cracked.

table 3

The glass components of Examples 17 to 24 include, in terms of mass percentage: SiO ₂ 56% to 65%, Al ₂ O ₃ 20% to 25%, K ₂ O 0 to 1.5%, MgO 0.5% to 3.5%, Na ₂ O 3.5% ~ 6%, Li ₂ O 2% ~ 5%, ZrO ₂ 2% ~ 4%, B ₂ O ₃ 0 ~ 2%, P ₂ O ₅ 0.5% ~ 1%, ZnO 0 ~ 1% And TiO ₂ 1% ~ 3.5%. The surface Vickers hardness of the precursor glass is 576Hv to 635Hv. After nucleation and crystallization treatment, the phase composition of glass-ceramics in terms of mass percentage includes: 52% to 90% β-spodumene crystal phase, 0 to 30% eucryptite crystal phase and 10% to 10% β-spodumene crystal phase. 20% glass phase; the appearance of crystallized glass is transparent or translucent, and the average transmittance from 400 to 780nm is 69.5% to 91.8%. After two-step chemical strengthening treatment, the surface stress value of the glass (K-Na compressive stress CS) is 979MPa ~ 1045MPa, and the deep stress depth (Li-Na exchange stress depth Dol-Na) is 148.4μm ~ 156.4μm. The surface Vickers hardness of the strengthened glass-ceramic is ≥773Hv, the 180-mesh surface ball drop height is ≥1.8m, the ring pressure strength is ≥653MPa, and the broken appearance is cracked.

Referring to Figure 3, which is an XRD pattern of the crystallized glass of Example 19, it can be seen that the crystallized glass of Example 19 has characteristic peaks of β-spodumene and eucryptite.

Table 4

The glass components or crystal phases of the crystallized glass of Comparative Examples 1 to 8 are different from those of Examples 1 to 24. The surface Vickers hardness of the precursor glass is 576Hv to 635Hv. The appearance of crystallized glass is transparent or translucent, with an average transmittance of 69.5% to 91.8% from 400 to 780nm. After two-step chemical strengthening treatment, the surface stress value of the glass (K-Na compressive stress CS) is 673MPa ~ 1141MPa, and the deep stress depth (Li-Na exchange stress depth Dol-Na) is 121μm ~ 137μm. The surface Vickers hardness of the strengthened glass-ceramic is 692Hv~732Hv, the 180-mesh surface ball drop height is 1.4m~1.9m, and the ring pressure strength is 490MPa~623MPa. The mechanical properties of the strengthened glass-ceramics are inferior to those of Examples 1 to 24, and the strengthened glasses of Comparative Examples 1 to 3 and 7 are pulverized after being broken, and the resulting fragments are smaller in size.

Refer to Figures 4 and 5. Figure 4 is an appearance view of the tempered glass of Example 1 after it is broken. Figure 5 is an appearance view of the tempered glass of Comparative Example 1 after it is broken. It can be seen that the appearance of the tempered glass of Example 1 after it is broken. The size of the fragments is larger and the range is smaller; while the fragments produced after the strengthened glass of Comparative Example 1 is broken are smaller in size, and the cracks are all over the entire glass, affecting the continued use of the glass product.

The technical features of the above-described embodiments can be combined in any way. To simplify the description, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, All should be considered to be within the scope of this manual.

The above-described embodiments only express several implementation modes of the present application, and their descriptions are relatively specific and detailed, but they should not be construed as limiting the scope of the patent application. It should be noted that, for those of ordinary skill in the art, several modifications and improvements can be made without departing from the concept of the present application, and these all fall within the protection scope of the present application. Therefore, the protection scope of this patent application should be determined by the appended claims.

Claims

A kind of crystallized glass, characterized in that, in terms of mass percentage, its components include:

Wherein, the crystal phase of the crystallized glass includes β-spodumene.
The crystallized glass according to claim 1, characterized in that the crystallization degree of the crystallized glass is ≥55%.
The crystallized glass according to claim 1 or 2, characterized in that the mass content of the β-spodumene in the crystallized glass is 23% to 90%.
The crystallized glass according to any one of claims 1 to 3, characterized in that the crystal phase of the crystallized glass further includes eucryptite.
The crystallized glass according to claim 4, wherein the mass content of the eucryptite in the crystallized glass is ≤32%.
The crystallized glass according to any one of claims 1 to 5, characterized in that the crystallized glass satisfies at least one of the conditions (1) to (11):

(1) The mass content of SiO 2 is 54% to 63%;

(2) The mass content of Al 2 O 3 is 18% to 27%;

(3) The mass content of K 2 O is 0 to 1.5%;

(4) The mass content of MgO is 0.5% to 3.5%;

(5) The mass content of Na 2 O is 3.5% to 6%;

(6) The mass content of Li 2 O is 3% to 6.5%;

(7) The mass content of ZrO 2 is 1% to 4%;

(8) The mass content of B 2 O 3 is 0 to 3%;

(9) The mass content of P 2 O 5 is 0.5% to 1%;

(10) The mass content of ZnO is 0 to 1%;

(11) The mass content of TiO 2 is 1% to 4%.
A method for preparing crystallized glass according to any one of claims 1 to 6, characterized in that it includes the following steps:

Prepare raw materials according to the components of the crystallized glass;

Melt the raw materials into clear glass liquid;

Shape the clarified glass liquid to prepare precursor glass;

The precursor glass is sequentially subjected to nucleation treatment and crystallization treatment to prepare the crystallized glass.
The method for preparing crystallized glass according to claim 7, wherein the temperature of the nucleation treatment is 630°C to 700°C; the time of the nucleation treatment is 2h to 10h;

The temperature of the crystallization treatment is 780°C to 830°C; the time of the crystallization treatment is 0.5h to 4h.
A kind of tempered glass, characterized in that it is obtained by chemically strengthening the crystallized glass according to any one of claims 1 to 6.
The strengthened glass according to claim 9, characterized in that the surface stress value of the strengthened glass is ≥ 645 MPa, and the deep stress depth Dol-Na ≥ 138 μm.
The tempered glass according to claim 9 or 10, characterized in that the tempered glass satisfies at least one of the conditions (i) to (iii):

(i) The surface Vickers hardness of the strengthened glass is ≥730Hv;

(ii) The ring crushing strength of the strengthened glass is ≥650N;

(iii) The drop height of 180-grit sandpaper for the tempered glass is ≥1.5m.
A method for preparing strengthened glass according to any one of claims 9 to 11, characterized in that it includes the following steps:

The crystallized glass is subjected to a first strengthening treatment in a first molten salt; in terms of mass percentage, the first molten salt includes 40% to 60% sodium nitrate and 40% to 60% potassium nitrate;

The crystallized glass that has undergone the first strengthening treatment is subjected to a second strengthening treatment in a second molten salt; in terms of mass percentage, the second molten salt includes 0 to 4% sodium nitrate and 96% to 100 % potassium nitrate.
The method for preparing tempered glass according to claim 12, wherein the temperature of the first strengthening treatment is 440°C to 500°C; the time of the first strengthening treatment is 4h to 16h;

The temperature of the second strengthening treatment is 380°C to 420°C; the time of the second strengthening treatment is 1h to 4h.
Application of the tempered glass according to any one of claims 9 to 11 in the preparation of electronic products.
An electronic product, characterized in that it includes a main body and a protective glass fitted to the main body, and the protective glass is the tempered glass according to any one of claims 9 to 11.