阅读说明：本技术 锂锆质铝硅酸盐玻璃、强化玻璃及其制备方法和显示器件 (Lithium-zirconium aluminosilicate glass, tempered glass, preparation methods of lithium-zirconium aluminosilicate glass and tempered glass, and display device ) 是由 平文亮 周翔磊 肖子凡 王琰 刘红刚 陈志鸿 何进 于 2019-10-10 设计创作，主要内容包括：本发明涉及一种锂锆质铝硅酸盐玻璃、强化玻璃及其制备方法和显示器件。按质量百分比计,锂锆质铝硅酸盐玻璃包括如下组分：SiO<Sub>2</Sub>50％～72％,Al<Sub>2</Sub>O<Sub>3</Sub>10％～27％,B<Sub>2</Sub>O<Sub>3</Sub>0.1％～10.0％,Li<Sub>2</Sub>O 2％～10％,Na<Sub>2</Sub>O 4％～15％,ZrO<Sub>2</Sub>0.1％～5.0％及K<Sub>2</Sub>O 0～4％,其中,Li<Sub>2</Sub>O、Na<Sub>2</Sub>O和K<Sub>2</Sub>O的总质量百分比大于或等于9％,ZrO<Sub>2</Sub>和Al<Sub>2</Sub>O<Sub>3</Sub>的总质量百分比大于10％,且Li<Sub>2</Sub>O的质量与Li<Sub>2</Sub>O、Na<Sub>2</Sub>O和K<Sub>2</Sub>O三者总质量的比为(0.22～0.48)∶1。上述锂锆质铝硅酸盐玻璃经强化后的抗弯强度大于700MPa,承受的落球能量超过0.4J。(The invention relates to lithium-zirconium aluminosilicate glass, tempered glass, preparation methods of lithium-zirconium aluminosilicate glass and tempered glass, and a display device. The lithium zirconium aluminosilicate glass comprises the following components in percentage by mass: SiO 2 2 50％～72％，Al 2 O 3 10％～27％，B 2 O 3 0.1％～10.0％，Li 2 O 2％～10％，Na 2 O 4％～15％，ZrO 2 0.1% -5.0% and K 2 0 to 4% of O, wherein Li 2 O、Na 2 O and K 2 O is 9% or more in total, ZrO 2 And Al 2 O 3 Is greater than 10% by mass, and Li 2 Mass of O and Li 2 O、Na 2 O and K 2 The total mass ratio of the O to the N is (0.22-0.48) to 1. The above lithium zirconiumThe bending strength of the strengthened aluminosilicate glass is more than 700MPa, and the falling ball energy born by the aluminosilicate glass exceeds 0.4J.)

1. The lithium-zirconium aluminosilicate glass is characterized by comprising the following components in percentage by mass:

wherein, the Li₂O, said Na₂O and said K₂O is 9% or more in total mass%, and ZrO₂And said Al₂O₃Is greater than 10% by mass, and the Li₂Mass of O and Li₂O, said Na₂O and said K₂The total mass ratio of the O to the N is (0.22-0.48) to 1.

2. The lithium zirconium aluminosilicate glass of claim 1, wherein the lithium zirconium aluminosilicate glass comprises, in mass percent: SiO 2₂ 55％～67％，Al₂O₃ 13％～25％，B₂O₃0.5％～4％，Li₂O 3％～7％，Na₂O 6％～12％，ZrO₂1% -4% and K₂0 to 3% of O, wherein the Li₂O, said Na₂O and said K₂O is 9% or more in total mass%, and ZrO₂And said Al₂O₃Is greater than 16% and the Li₂Mass of O and Li₂O, said Na₂O and said K₂The total mass ratio of the O to the N is (0.27-0.41) to 1.

3. The lithium zirconium aluminosilicate of claim 2Salt glass, characterized in that the lithium zirconium aluminosilicate glass comprises, in mass percent: SiO 2₂ 58％～64％，Al₂O₃ 16％～22％，B₂O₃1％～2％，Li₂O 4％～6％，Na₂O 8％～10％，ZrO₂3% -4% and K₂0 to 2% of O, wherein the Li₂O, said Na₂O and said K₂O is greater than or equal to 12 percent in total mass percent, and the ZrO₂And said Al₂O₃Is greater than 19.5%, and the Li₂Mass of O and Li₂O, said Na₂O and said K₂The total mass ratio of the O to the N is (0.29-0.38) to 1.

4. The lithium zirconium aluminosilicate glass of any one of claims 1 to 3, wherein the lithium zirconium aluminosilicate glass further comprises, in mass percent, not more than 6% MgO; and/or the presence of a catalyst in the reaction mixture,

the lithium zirconium aluminosilicate glass further comprises, in mass percent, not more than 4% CaO; and/or the presence of a catalyst in the reaction mixture,

the lithium zirconium aluminosilicate glass further comprises, in mass percent, not more than 4% SrO; and/or the presence of a catalyst in the reaction mixture,

the lithium zirconium aluminosilicate glass further comprises, in mass percent, no more than 4% ZnO; and/or the presence of a catalyst in the reaction mixture,

the lithium zirconium aluminosilicate glass also comprises TiO not more than 2 percent by mass₂。

5. The lithium zirconium aluminosilicate glass of any one of claims 1 to 3, wherein the lithium zirconium aluminosilicate glass further comprises, in mass percent, not more than 4% MgO; and/or the presence of a catalyst in the reaction mixture,

the lithium zirconium aluminosilicate glass further comprises, in mass percent, not more than 2% CaO; and/or the presence of a catalyst in the reaction mixture,

the lithium zirconium aluminosilicate glass further comprises, in mass percent, not more than 2% SrO; and/or the presence of a catalyst in the reaction mixture,

the lithium zirconium aluminosilicate glass further comprises, in mass percent, no more than 2% ZnO; and/or the presence of a catalyst in the reaction mixture,

the lithium zirconium aluminosilicate glass also comprises TiO not more than 1 percent by mass₂。

6. The lithium zirconium aluminosilicate glass of claim 4, wherein the lithium zirconium aluminosilicate glass further comprises not greater than 1% SnO by mass₂(ii) a And/or the presence of a catalyst in the reaction mixture,

the lithium zirconium aluminosilicate glass further comprises CeO not more than 0.5% by mass₂。

7. The lithium zirconium aluminosilicate glass of any one of claims 1 to 3, wherein the lithium zirconium aluminosilicate glass further comprises: MgO with the mass percent not more than 4 percent, ZnO with the mass percent not more than 2 percent and TiO with the mass percent not more than 1 percent₂SnO with mass percent not more than 0.5%₂And CeO with the mass percent not more than 0.5 percent₂。

8. A strengthened glass obtained by chemically strengthening the lithium zirconium aluminosilicate glass according to any one of claims 1 to 7.

9. A preparation method of tempered glass is characterized by comprising the following steps: firstly, the lithium zirconium aluminosilicate glass of any one of claims 1 to 7 is subjected to NaNO treatment at a temperature of 390 to 420 ℃ and a mass ratio of 2: 8 to 8: 2₃And KNO₃The mixed molten liquid is toughened for 2 to 6 hours and then NaNO with the temperature of 380 to 400 ℃ and the mass ratio of 0.1: 99.9 to 15: 85₃And KNO₃The mixed molten liquid is toughened for 2 to 4 hours to obtain the strengthened glass.

10. A display device comprising the lithium zirconium aluminosilicate glass according to any one of claims 1 to 7 or the strengthened glass according to claim 8 or the strengthened glass produced by the method for producing the strengthened glass according to claim 9.

Technical Field

The invention relates to the field of glass, in particular to lithium zirconium aluminosilicate glass, tempered glass, preparation methods of the lithium zirconium aluminosilicate glass and the tempered glass, and a display device.

Background

The thin plate glass is a member for protecting a display panel of a display device without affecting its display effect. There are many display devices such as a portable phone, a Personal Digital Assistant (PDA), a digital camera, a Flat Panel Display (FPD), and the like. In recent years, with the trend toward thinner and more functional display devices such as cellular phones and PDAs, higher demands have been made on the mechanical strength of glass. Therefore, generally, the thin glass sheet is further chemically strengthened to obtain a tempered glass. The tempered glass can be chemically strengthened by ion exchange treatment, and sodium ions and lithium ions on the surface of the glass are exchanged with potassium ions or sodium ions in an ion exchange salt to form a compressive stress layer on the surface of the glass.

The traditional glass cover plate market mainly takes (boron) aluminum silicon glass and lithium (boron) aluminum silicon glass as main materials, such as Gorilla glass of corning, T2X-1 of NEG, dragon mark glass of Asahi glass, panda glass of Asahi rainbow and KK3 glass of south glass in China, but the traditional glass is still low in strength and cannot play a good protection role when being used for protecting glass of mobile equipment.

Disclosure of Invention

Accordingly, there is a need for a lithium zirconium aluminosilicate glass having high strength.

In addition, the tempered glass, the preparation method of the tempered glass and the display device are also provided.

The lithium-zirconium aluminosilicate glass comprises the following components in percentage by mass:

wherein, the Li₂O, said Na₂O and said K₂O is 9% or more in total mass%, and ZrO₂And said Al₂O₃Is greater than 10% by mass, and the Li₂Mass of O and Li₂O, said Na₂O and said K₂The total mass ratio of the O to the N is (0.22-0.48) to 1.

In one embodiment, the lithium zirconium aluminosilicate glass comprises, in mass percent: SiO 2₂55％～67％，Al₂O₃ 13％～25％，B₂O₃ 0.5％～4％，Li₂O 3％～7％，Na₂O 6％～12％，ZrO₂1% -4% and K₂0 to 3% of O, wherein the Li₂O, said Na₂O and said K₂O is 9% or more in total mass%, and ZrO₂And said Al₂O₃Is greater than 16% and the Li₂Mass of O and Li₂O, said Na₂O and said K₂The total mass ratio of the O to the N is (0.27-0.41) to 1.

In one embodiment, the lithium zirconium aluminosilicate glass comprises, in mass percent: SiO 2₂58％～64％，Al₂O₃ 16％～22％，B₂O₃ 1％～2％，Li₂O 4％～6％，Na₂O 8％～10％，ZrO₂3% -4% and K₂0 to 2% of O, wherein the Li₂O, said Na₂O and said K₂O is greater than or equal to 12 percent in total mass percent, and the ZrO₂And said Al₂O₃Is greater than 19.5%, and the Li₂Mass of O and Li₂O, said Na₂O and said K₂The total mass ratio of the O to the N is (0.29-0.38) to 1.

In one embodiment, the lithium zirconium aluminosilicate glass further comprises, in mass percent, no more than 6% MgO; and/or the presence of a catalyst in the reaction mixture,

the lithium zirconium aluminosilicate glass further comprises, in mass percent, not more than 4% CaO; and/or the presence of a catalyst in the reaction mixture,

the lithium zirconium aluminosilicate glass further comprises, in mass percent, not more than 4% SrO; and/or the presence of a catalyst in the reaction mixture,

the lithium zirconium aluminosilicate glass further comprises, in mass percent, no more than 4% ZnO; and/or the presence of a catalyst in the reaction mixture,

the lithium zirconium aluminosilicate glass also comprises TiO not more than 2 percent by mass₂。

In one embodiment, the lithium zirconium aluminosilicate glass further comprises, in mass percent, no more than 4% MgO; and/or the presence of a catalyst in the reaction mixture,

the lithium zirconium aluminosilicate glass further comprises, in mass percent, not more than 2% CaO; and/or the presence of a catalyst in the reaction mixture,

the lithium zirconium aluminosilicate glass further comprises, in mass percent, not more than 2% SrO; and/or the presence of a catalyst in the reaction mixture,

the lithium zirconium aluminosilicate glass further comprises, in mass percent, no more than 2% ZnO; and/or the presence of a catalyst in the reaction mixture,

the lithium zirconium aluminosilicate glass also comprises TiO not more than 1 percent by mass₂。

In one embodiment, the lithium zirconium aluminosilicate glass further comprises not more than 1% SnO by mass₂(ii) a And/or the presence of a catalyst in the reaction mixture,

the lithium zirconium aluminosilicate glass further comprises CeO not more than 0.5% by mass₂。

In one embodiment, the lithium zirconium aluminosilicate glass further comprises not more than 0.5% SnO by mass₂。

In one embodiment, the lithium zirconium aluminosilicate glass further comprises: MgO with the mass percent not more than 4 percent, ZnO with the mass percent not more than 2 percent and TiO with the mass percent not more than 1 percent₂SnO with mass percent not more than 0.5%₂And CeO with the mass percent not more than 0.5 percent₂。

A strengthened glass is obtained by chemically strengthening the lithium zirconium aluminosilicate glass.

A preparation method of tempered glass comprises the following steps: firstly, the lithium zirconium aluminosilicate glass is subjected to NaNO treatment at the temperature of 390-420 ℃ and the mass ratio of 2: 8-8: 2₃And KNO₃The mixed molten liquid is toughened for 2 to 6 hours and then NaNO with the temperature of 380 to 400 ℃ and the mass ratio of 0.1: 99.9 to 15: 85₃And KNO₃The mixed molten liquid is toughened for 2 to 4 hours to obtain the strengthened glass.

A display device comprising the above lithium zirconium aluminosilicate glass or the above tempered glass or a tempered glass produced by the above method for producing a tempered glass.

The lithium zirconium aluminosilicate glass is prepared by controlling the components and the composition of the glass and regulating Li₂O、Na₂O and K₂The total mass percent of O is more than or equal to 9 percent, and Li₂Mass of O and Li₂O、Na₂O and K₂The ratio of the sum of the masses of O is 0.22 to 0.48, ZrO is added₂And Al₂O₃Is more than 10 percent by mass, thereby obtaining the lithium zirconium aluminosilicate glass. The strength of the strengthened glass obtained by chemically strengthening the lithium zirconium aluminosilicate glass is greatly improved, the bending strength after chemical strengthening is more than 700MPa, and the born falling ball energy exceeds 0.4J, so that the lithium zirconium aluminosilicate glass can well protect mobile equipment when used for protecting glass of the mobile equipment.

Drawings

FIG. 1 is a process flow diagram of one embodiment of a method of making a lithium zirconium aluminosilicate glass;

FIG. 2 is a process flow diagram of a method of making a strengthened glass according to one embodiment.

Detailed Description

In order that the invention may be more fully understood, reference will now be made to the following description taken in conjunction with the accompanying drawings. The detailed description sets forth the preferred embodiments of the invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

An embodiment of the lithium zirconium aluminosilicate glass comprises the following components in percentage by mass:

wherein Li₂O、Na₂O and K₂O is 9% or more in total, ZrO₂And Al₂O₃Is greater than 10% by mass, and Li₂Mass of O and Li₂O、Na₂O and K₂The total mass ratio of the O to the N is (0.22-0.48) to 1.

In one embodiment, the lithium zirconium aluminosilicate glass further comprises MgO, CaO, SrO, ZnO and TiO₂At least one of (1). Specifically, the mass percentage of MgO is not more than 6%. CaO in a mass percent ofOver 4%. The mass percentage of SrO is not more than 4%. The mass percent of ZnO is not more than 4 percent. TiO 2₂Is not more than 2% by mass.

Further, the mass percentage of MgO is not more than 4%. The mass percent of CaO is not more than 2%. The mass percentage of SrO is not more than 2 percent. The mass percent of ZnO is not more than 2 percent. TiO 2₂Is not more than 1% by mass.

Still further, the lithium zirconium aluminosilicate glass further comprises: MgO, ZnO and TiO₂Wherein the mass percent of MgO is not more than 2%, the mass percent of ZnO is not more than 2%, and TiO₂Is not more than 1% by mass.

In one embodiment, the lithium zirconium aluminosilicate glass further comprises not more than 1% SnO by mass₂. Further, SnO₂Is not more than 0.5 percent.

In another embodiment, the lithium zirconium aluminosilicate glass further comprises, in mass percent, not more than 0.5% CeO₂。

Further preferably, the lithium zirconium aluminosilicate glass comprises: SiO 2₂ 50％～72％，Al₂O₃ 10％～27％，B₂O₃ 0.1％～10.0％，Li₂O 2％～10％，Na₂O 4％～15％，ZrO₂ 0.1％～5.0％，K₂0-4% of O, MgO with the mass percent not more than 4%, ZnO with the mass percent not more than 2%, and TiO with the mass percent not more than 1%₂SnO with mass percent not more than 1%₂And CeO with the mass percent not more than 0.5 percent₂. Wherein Li₂O、Na₂O and K₂O is 9% or more in total, ZrO₂And Al₂O₃Is greater than 10% by mass, and Li₂Mass of O and Li₂O、Na₂O and K₂The total mass ratio of the O to the N is (0.22-0.48) to 1.

In the present embodiment, the lithium zirconium aluminosilicate glass does not contain P₂O₅And Fe₂O₃. No P addition to lithium zirconium aluminosilicate glasses₂O₅Can avoid adding P₂O₅And B₂O₃The P-B phase separation opacification phenomenon is generated, the haze (namely the opacity degree) is increased, and the chemical stability of the glass is reduced.

SiO₂(silica) is an important glass-forming oxide and is an essential component for forming a glass skeleton. SiO 2₂The strength, chemical stability and the like of the glass can be improved, and the glass can obtain higher strain point and lower thermal expansion coefficient. In the present embodiment, SiO₂The mass percentage of (b) is preferably 50 to 72%. More preferably 55% to 67%. Most preferably 58% to 64%. If SiO₂The mass percent of (A) is less than 50%, the glass main body network structure is poor, the mechanical property is poor, and the weather resistance is poor. If SiO₂The mass percent of the silica-alumina composite glass is over 72 percent, the melting temperature of the glass in the production process is too high, the energy consumption is increased, the defects of frequent bubbles, stones and the like are easily caused, meanwhile, the proportion of the silica-alumina framework structure is higher, the network gaps are smaller, the chemical strengthening ion exchange is not facilitated, and the chemical strengthening efficiency is influenced. Therefore, in the present embodiment, SiO₂The mass percentage of (A) is set to 50-72%.

Al₂O₃(aluminum oxide) can participate in network formation, plays a role of a network formation body, can reduce the crystallization tendency of glass, and can improve the chemical stability, thermal stability, mechanical strength and hardness of the glass, and meanwhile, Al₂O₃And is also an essential component for increasing the modulus of elasticity of the drawn glass. But Al₂O₃The addition of (b) increases the viscosity of the glass. If Al is present₂O₃Too much mass percent of (b) makes it difficult to obtain glass with long material properties, making glass shaping difficult. Further, Al in the glass³⁺Tend to form an alundum tetrahedral network (AlO)₄]This is compared to the silicon-oxygen tetrahedron [ SiO ]₄]The network is much larger, leaving larger voids as channels for ion diffusion, and therefore high Al in the glass₂O₃The amount promotes the rate of migration and replacement of alkali metal ions. A. thel₂O₃The higher the content is, the larger the gaps of the skeleton network is, the more favorable the ion exchange is, however, the thermal expansion coefficient can not be further reduced because of the overhigh content, and on the contrary, the high-temperature viscosity of the glass is obviously increased, the melting temperature in the production process is overhigh, the energy consumption is increased, and the defects of controlling bubbles, stones and the like are also not facilitated. However, Al₂O₃At lower contents, the network space becomes smaller, which is detrimental to ion transport and seriously affects the efficiency of chemical enhancement. Therefore, in the present embodiment, Al₂O₃The mass percentage of (b) is preferably 10% to 27%. Al (Al)₂O₃The mass percentage of (b) is more preferably 13 to 25%. Al (Al)₂O₃The mass percentage of (b) is most preferably 16% to 22%.

B₂O₃(boron oxide) is one of the important components of the boroaluminosilicate glass, belongs to a formed oxide, and can reduce the thermal expansion coefficient of the aluminosilicate glass and improve the thermal stability and the chemical stability of the aluminosilicate glass. B is₂O₃Too high a content of (A) and boron volatilization at high temperature is severe due to its viscosity-reducing effect, while B₂O₃Too high content of (A) can narrow the forming temperature, and bring difficulty to the precision control of wall thickness and pipe diameter in the tube drawing and forming of the boron-aluminum silicate glass; in addition when B₂O₃When the amount of introduction is too high, boron oxygen trigonal [ BO ] is introduced₃]Increasing the expansion coefficient of the boron-aluminum silicate glass, and the like, but increasing the expansion coefficient, and the like, causing an abnormal phenomenon, B₂O₃At too high a content, the ion exchange capacity of the glass is significantly reduced. Therefore, in the present embodiment, B₂O₃The content of (b) is preferably 0.1 to 10.0% by mass. B is₂O₃The mass percentage of (b) is more preferably 0.5% to 4.0%. B is₂O₃The mass percentage of (b) is most preferably 1% to 2%.

Li₂O (lithium oxide) is an ideal flux and is a main component for ion exchange, since Li⁺Has a polarization characteristic of effectively reducing high-temperature viscosity at high temperature, and Li⁺Has a small radius, can be filled in vitreous air and balance freeOxygen, suitably Li₂O can obviously enhance the mechanical strength, the surface hardness, the chemical resistance and the like of the glass body. Because the embodiment uses NaNO in the strengthening process₃With KNO₃Mixed molten salt of (2), by Li in glass⁺With Na in the molten salt⁺The ion exchange is carried out, so that the depth of the compressive stress layer can be increased in a short time, and the glass has more excellent mechanical impact resistance. Li₂The mass percentage of O is preferably 2% to 10%. Li₂The mass percentage of O is more preferably 3% to 7%. Li₂The mass percentage of O is most preferably 4 to 6%. If the mass percentage is less than 2%, the glass basically has difficulty in obtaining higher stress layer depth; if the content is more than 10 percent, the manufacturing cost of the glass is increased, the expansion coefficient of the glass is obviously increased, the crystallization tendency of the glass is too high, and the probability of generating stone defects of the glass is obviously increased.

Na₂O (sodium oxide) is an exo-oxide of the boroaluminosilicate glass network and provides free oxygen to break Si-O bonds, thereby lowering the viscosity and melting temperature of the aluminosilicate glass. Na (Na)₂Too high content of O increases linear thermal expansion coefficient and decreases chemical stability, and Na₂The amount of O volatilized increases, resulting in non-uniformity of the aluminosilicate glass composition. Na (Na)₂The content of O is too low to facilitate melting and forming of the glass, and is not conducive to chemical exchange between Na ions and K ions to form a compressive stress layer on the surface of the glass, thereby achieving the purpose of enhancing the mechanical strength of the glass₂The O component plays a role in exchanging with K ions in molten liquid to form pressure stress on the surface of the glass during tempering, and directly influences the strength performance of the glass. Therefore, in the present embodiment, Na₂The mass percentage of O is preferably 4 to 15%. Na (Na)₂The mass percentage of O is more preferably 6% to 12%. Na (Na)₂The mass percentage of O is most preferably 8 to 10%.

K₂O (potassium oxide) and Na₂O is an alkali metal oxide and acts similarly in the glass structure, with a small amount of K₂Substitution of O for Na₂O can play the 'mixed alkali effect' to improve a series of performances of the glass, and is used for improvingMelt properties and components for increasing the rate of ion exchange in chemical strengthening to achieve the desired surface compressive stress and depth of stress layer. If K₂If the content of O is too high, the weather resistance is lowered. In this embodiment, the inventors analyzed the content of alkali metal in the glass to determine K₂The mass percentage of O is set to be 0-4%. K₂The mass percentage of O is more preferably 0 to 3%. K₂The most preferable mass percentage of O is 0-2%.

ZrO₂In silicate glasses mainly cubic [ ZrO ]₈]The coordination form exists, because the ionic radius is larger, the coordination form belongs to a network exosome in the glass structure, and the solubility of the coordination form in the glass is smaller, the viscosity of the glass can be obviously increased, so the addition amount of the coordination form is not more than 5 percent, and ZrO is not suitable to be added₂Can improve the acid and alkali resistance and the refractive index of the glass. In the present embodiment, ZrO₂The mass percentage of (b) is preferably 0.1 to 5.0%. ZrO (ZrO)₂The mass percentage of (b) is more preferably 1% to 4%. ZrO (ZrO)₂The mass percentage of (b) is most preferably 3% to 4%.

MgO (magnesium oxide) is a network exoxide, and MgO helps to lower the melting point of glass, lower the viscosity of glass at high temperature, promote melting and clarification of glass, improve uniformity and increase hydrolysis resistance. MgO stabilizes the glass, improves the durability of the glass, prevents the glass from crystallizing, and suppresses the movement of alkali metal ions in the glass, and similarly has a function of improving the elastic modulus of the glass. MgO enhances the stability of the glass network space at low temperature and lowers the thermal expansion coefficient of the glass to some extent, but it has an effect of inhibiting ion exchange, so in the present embodiment, MgO is not an essential component and can be omitted. In the present embodiment, the mass percentage of MgO is preferably 0 to 6%. The MgO is more preferably 0 to 4% by mass. The mass percentage of MgO is most preferably 0-2%. If the MgO content is higher than 6% by mass, Mg²⁺The ion exchange capacity of the glass is severely hindered, resulting in a significant reduction in the depth of the compressive stress layer.

CaO (calcium oxide) makes silicon-oxygen tetrahedron [ SiO ]₄]The formed network is relaxed, broken and the glass is improvedAlthough the glass is not easily devitrified or melted at a high temperature, the weather resistance of the aluminosilicate glass is affected by an excessive content thereof, and the progress of ion exchange is seriously inhibited. The preferable mass percentage of CaO is 0-4%. The preferable mass percentage of CaO is 0 to 2%.

SrO (strontium oxide) and calcium oxide and magnesium oxide are similar in that they can lower the high-temperature viscosity of the glass and facilitate melting, but because of their large ionic radius, they do not hinder the Li-Na-K ion exchange process in the glass structure, so that a small amount of strontium oxide is used to replace part of the calcium oxide and magnesium oxide. In the present embodiment, the mass percentage of SrO is preferably 0 to 4%. The mass percentage of SrO is more preferably 0-2%. In the present embodiment, SrO may be omitted.

ZnO (zinc oxide) belongs to a divalent metal oxide array, also has the function of an alkaline earth metal oxide, and partial ZnO materials are added into a silicate glass system, so that the melting temperature of glass can be effectively reduced, the transition temperature Tg of the glass is reduced, and the alkali resistance of a glass substrate can be improved; in aluminosilicate glass bodies, Zn is often in [ ZnO ]₆]And [ ZnO ]₄]Of the two ligands, [ ZnO ]₄]The invention adopts partial zinc oxide to replace calcium oxide and magnesium oxide, which is beneficial to maintaining the chemical stability of the glass and promoting the rapid proceeding of ion exchange. The preferable mass percentage of ZnO is 0-4%. The ZnO content is more preferably 0 to 2% by mass. In this embodiment, ZnO may be omitted.

TiO₂With ZrO₂Similarly, the glass belongs to transition elements, has certain coloring capability, shows yellow color, and can improve the chemical stability of the glass and the color temperature of the glass. Therefore, TiO is used in this embodiment₂The mass percentage of (B) is preferably 0 to 2%. TiO 2₂The content of (b) is more preferably 0 to 1% by mass. In this embodiment, TiO₂The components are not essential and may be omitted.

SnO₂And CeO₂The glass often exists in a plurality of valence states in the glass body, can increase the uvioresistant performance of the glass, prevent the color change caused by the valence change of coloring ions, and can increase the high-temperature bubble-removing capability of the glass body by adding the glass body singly or in a mixture way, thereby being a commonly used clarifying agent. In this embodiment, SnO₂The mass percentage of (B) is preferably 0 to 1%. SnO₂The mass percentage of (b) is more preferably 0 to 0.5%. CeO (CeO)₂The mass percentage of (A) is preferably 0-0.5%. In this embodiment, SnO₂And CeO₂None of them are essential components and may be omitted.

Mixing Li₂O、Na₂O and K₂The effect of setting the total mass percentage of O to be greater than or equal to 9% is: the alkali metal is taken as a typical glass network modifier which can obviously lower the melting temperature of the glass, and in addition, the alkali metal ions are the key of whether the glass can realize ion exchange through chemical strengthening so as to obtain a sufficient compressive stress layer on the surface of the glass, and the comprehensive consideration is that Li₂O、Na₂O and K₂The total mass percentage of O is required to be greater than or equal to 9 percent.

Mixing Li₂Mass of O and Li₂O、Na₂O and K₂The total mass ratio of the O to the O is set to be (0.22-0.48) to 1, and the effects are as follows: the alkali metal is the key for realizing high-performance chemical strengthening of the glass, the effects of the alkali metal in the chemical strengthening process are different, a certain proportion of Li element is needed in the glass body, the Li element can exchange Na ions and partial K ions in tempering salt in the first step of chemical strengthening process, a stress gradient compressive stress layer is formed on the surface of the glass due to the volume difference of the ions, and the glass has the performance of increasing the strength and toughness of the glass only by the depth of a relatively deep stress layer, and long-term tests show that the Li element has different effects in the chemical strengthening process₂O accounts for more than 22 percent of the total alkali metal content, and is not suitable to exceed 48 percent. Li₂The proportion of O in the total alkali metal affects the tempering performance, and Li₂Li with the same mass percentage due to smaller relative molecular mass of O₂O relative to Na₂O and K₂O has more mole number, which can sharply reduce the melting temperature of the glass, is not beneficial to production control,and excessive Li₂O causes devitrification of the glass, so Li₂The proportion of O in the alkali metal should not exceed 48%.

ZrO 2 is mixed with₂And Al₂O₃The effect of setting the total mass percentage of (a) to be more than 10% is: ZrO (ZrO)₂And Al₂O₃The invention is a key component for realizing the speed and the difficulty of alkali metal ion exchange in the chemical toughening process, which is used as a network intermediate and partially participates in a glass network framework and macromolecular ZrO₂The material is filled in the network gaps, forms loose structural channels for alkali metal ion exchange, is beneficial to the ion exchange in the depth direction of the glass, thereby forming high stress depth and high surface stress, and simultaneously ZrO₂And Al₂O₃The components can increase the chemical stability of the glass, so the total mass percent of the glass is more than 10 percent.

In some of the embodiments, preferably, the lithium zirconium aluminosilicate glass comprises, in mass percent: SiO 2₂55％～67％，Al₂O₃ 13％～25％，B₂O₃ 0.5％～4％，Li₂O 3％～7％，Na₂O 6％～12％，ZrO₂1% -4% and K₂0-3% of O. Wherein Li₂O、Na₂O and K₂O is 9% or more in total, ZrO₂And Al₂O₃Is greater than 16% by mass, and Li₂Mass of O and Li₂O、Na₂O and K₂The total mass ratio of the O to the N is (0.27-0.41) to 1.

In this embodiment, the lithium zirconium aluminosilicate glass may further include: MgO, CaO, SrO, ZnO and TiO₂At least one of (1). Specifically, the mass percentage of MgO is not more than 6%. The mass percent of CaO is not more than 4%. The mass percentage of SrO is not more than 4%. The mass percent of ZnO is not more than 4 percent. TiO 2₂Is not more than 2% by mass.

Furthermore, the mass percent of MgO is not more than 4%, the mass percent of CaO is not more than 2%, the mass percent of SrO is not more than 2%, and the mass percent of ZnO is not more than 4%More than 2%, TiO₂Is not more than 1% by mass.

In this embodiment, the lithium zirconium aluminosilicate glass may further include: SnO₂And CeO₂At least one of (1). Wherein SnO₂The mass percentage of (A) is not more than l%. Further, SnO₂Is not more than 0.5 percent. CeO (CeO)₂Is not more than 0.5 percent.

Further preferably, in this embodiment, the lithium zirconium aluminosilicate glass comprises: SiO 2₂ 55％～67％，Al₂O₃13％～25％，B₂O₃ 0.5％～4％，Li₂O 3％～7％，Na₂O 6％～12％，ZrO₂ 1％～4％，K₂0-3% of O, MgO with the mass percent not more than 4%, ZnO with the mass percent not more than 2%, and TiO with the mass percent not more than 1%₂SnO with mass percent not more than 1%₂And CeO with the mass percent not more than 0.5 percent₂. Wherein Li₂O、Na₂O and K₂O is 9% or more in total, ZrO₂And Al₂O₃Is greater than 16% by mass, and Li₂Mass of O and Li₂O、Na₂O and K₂The total mass ratio of the O to the N is (0.27-0.41) to 1.

In this example, MgO, CaO, SrO, ZnO and TiO were used₂、SnO₂And CeO₂And may be omitted.

In other embodiments, it is further preferred that the lithium zirconium aluminosilicate glass comprises, in mass percent: SiO 2₂ 58％～64％，Al₂O₃ 16％～22％，B₂O₃ 1％～2％，Li₂O 4％～6％，Na₂O 8％～10％，ZrO₂3% -4% and K₂0-2% of O. Wherein Li₂O、Na₂O and K₂O is 12% or more in total, ZrO₂And Al₂O₃Is greater than 19.5% by mass, and Li₂Mass of O and Li₂O、Na₂O and K₂The total mass ratio of the three components of O is (0.29-0.38) to 1.

In this embodiment, the lithium zirconium aluminosilicate glass may further include, in mass percent: MgO, CaO, SrO, ZnO and TiO₂At least one of (1). Specifically, the mass percentage of MgO is not more than 6%. The mass percent of CaO is not more than 4%. The mass percentage of SrO is not more than 4%. The mass percent of ZnO is not more than 4 percent. TiO 2₂Is not more than 2% by mass.

Furthermore, the mass percent of MgO is not more than 4%, the mass percent of CaO is not more than 2%, the mass percent of SrO is not more than 2%, the mass percent of ZnO is not more than 2%, and TiO₂Is not more than 1% by mass.

Further, in this embodiment, the lithium zirconium aluminosilicate glass may further include SnO₂And CeO₂At least one of (1). Wherein SnO₂Is not more than 0.5 percent. CeO (CeO)₂Is not more than 0.5 percent.

Further preferably, in this embodiment, the lithium zirconium aluminosilicate glass comprises: SiO 2₂ 58％～64％，Al₂O₃16％～22％，B₂O₃ 1％～2％，Li₂O 4％～6％，Na₂O 8％～10％，ZrO₂ 3％～4％，K₂0-2% of O, MgO with the mass percent not more than 4%, ZnO with the mass percent not more than 2%, and TiO with the mass percent not more than 1%₂SnO with mass percent not more than 1%₂And CeO with the mass percent not more than 0.5 percent₂. Wherein Li₂O、Na₂O and K₂O is 12% or more in total, ZrO₂And Al₂O₃Is greater than 19.5% by mass, and Li₂Mass of O and Li₂O、Na₂O and K₂The total mass ratio of the three components of O is (0.29-0.38) to 1.

In this example, MgO, ZnO and TiO were used₂、SnO₂And CeO₂And may be omitted.

One conventional technique discloses a glass composition containing a non-zero amount of P₂O₅And K₂O, and less than 1 mol%, Li₂O and B₂O₃、P₂O₅、SiO₂And Al₂O₃The ratio of the total amount of (A) to (B) is less than 0.074. In contrast, the lithium zirconium aluminosilicate glass according to the embodiment of the present invention does not contain P₂O₅Can avoid adding P₂O₅And B₂O₃Thereby generating P-B phase separation opacification, causing the increase of haze (namely, opacity degree) and containing P in the glass₂O₅The chemical stability of the glass, especially the attack of water vapor and acidic liquids on the glass, is reduced. In addition, Li in the examples of the present invention₂O and B₂O₃、P₂O₅、SiO₂And Al₂O₃Is generally higher than 0.074, Li₂The amount of O is also typically greater than Na₂The quantity of O fully exerts the advantages of Li ions in the glass body and Na ions and K ions in the tempering salt, so that the surface stress value of the lithium zirconium aluminosilicate glass in the embodiment is more than 800MPa and the depth is more than 130 mu m, and the bending strength and the energy limit of impact resistance of the glass are greatly increased.

In addition, another technology discloses thin lithium-aluminum-silicon glass, the central tension of the toughened glass is less than 50Mpa, the surface compressive stress of the glass is 600-1200 Mpa, and the bending strength of the glass can reach 500MPa, so that the depth of the stress layer of the glass is less than 50 microns. After the lithium zirconium aluminosilicate glass in the embodiment is strengthened, the depth of the stress layer needs to be more than 100 μm, which is far greater than the depth of the stress layer of the toughened glass in the above technology.

Another conventional technique is B₂O₃And ZrO₂Is lower than that of (B) in the present embodiment₂O₃And ZrO₂The content of the glass is more than 0.1 percent, and the glass participates in the framework forming the glass body structure, thereby being beneficial to the processing of the glass substrate in the later period, increasing the fracture toughness of the glass, and forming the surface stress value of more than 800MPa and the sum of the surface stress values after temperingThe 100 mu m depth still has a compressive stress value of over 55MPa, and the mechanical strength and the drop resistance of the glass are enhanced.

Therefore, the traditional glass cover plate can be rapidly and chemically tempered, a compression stress layer with the pressure greater than 600MPa is formed on the surface of the glass, the depth of the stress layer is generally higher than 35 microns, the depth of the stress layer of the lithium-aluminum-silicon glass can reach more than 100 microns through a special tempering process, and the purposes of increasing the mechanical strength, the shock resistance, the friction resistance, the sand and stone ground falling resistance and the like of the glass are facilitated. But the strength of conventional glass is still low.

The lithium zirconium aluminosilicate glass has at least the following advantages:

(1) the above-mentioned lithium zirconium aluminosilicate glass has a glass composition of 84.5X 10 at 20 ℃ to 300 ℃^-7～94.9×10^-7Coefficient of thermal expansion of (a); melting temperature T₂At 1543-1638 deg.C; glass transition temperature T_gAt 497 ℃ -586 ℃; after a special chemical toughening process, the glass has surface compressive stress CS0 of more than 800MPa, compressive stress CS10 of more than 230MPa at a depth of 10 mu m from the surface of the glass, compressive stress CS30 of more than 140MPa at a depth of 30 mu m from the surface, and maximum stress layer depth Dol0 generated by ion exchange is more than 136 mu m.

(2) The bending strength of the strengthened lithium zirconium aluminosilicate glass is more than 700MPa, the borne falling ball energy exceeds 0.4J, and the strengthened lithium zirconium aluminosilicate glass can be used as protective glass for mobile phones, tablet computers or other mobile intelligent devices.

Referring to fig. 1, a method for preparing a lithium zirconium aluminosilicate glass according to an embodiment is a method for preparing the lithium zirconium aluminosilicate glass, and specifically includes the following steps:

step S110: weighing the following raw materials in percentage by mass: SiO 2₂ 50％～72％，Al₂O₃ 10％～27％，B₂O₃ 0.1％～10.0％，Li₂O 2％～10％，Na₂O 4％～15％，ZrO₂0.1% -5.0% and K₂0 to 4% of O, wherein Li₂O、Na₂O and K₂O is 9% or more in total, ZrO₂And Al₂O₃Is greater than 10% by mass, and Li₂Mass of O and Li₂O、Na₂O and K₂The total mass ratio of the O to the N is (0.22-0.48) to 1.

Step S120: and mixing the raw materials, and melting to obtain the glass slurry.

In one embodiment, the temperature for melting in step S120 is 1650 ℃. The melting time is 8 h.

Step S130: and homogenizing the glass slurry.

In one embodiment, the temperature of the homogenization process in step S130 is 1500 ℃. The time for the homogenization treatment was 1 h.

Step S140: and forming the glass slurry, and then annealing to obtain the lithium zirconium aluminosilicate glass.

Specifically, in the step of molding the glass paste, a casting molding manner is adopted. In one embodiment, the homogenized glass slurry is poured on an iron mold preheated to 450 ℃ to solidify and shape the glass slurry.

In the above method for producing a lithium zirconium aluminosilicate glass, the glass can be obtained in a conventional process for producing a flat glass, and the production method is not limited to a float forming process, an overflow down-draw method, a drawing method, a flat-draw method, a rolling method, and the like.

The strengthened glass of an embodiment is obtained by chemically strengthening the lithium zirconium aluminosilicate glass of the above embodiment. Specifically, the lithium zirconium aluminosilicate glass includes, by mass percent: SiO 2₂ 50％～72％，Al₂O₃ 10％～27％，B₂O₃ 0.1％～10.0％，Li₂O 2％～10％，Na₂O 4％～15％，ZrO₂0.1% -5.0% and K₂0 to 4% of O, wherein Li₂O、Na₂O and K₂O is 9% or more in total, ZrO₂And Al₂O₃Is greater than 10% by mass, and Li₂Mass of O and Li₂O、Na₂O and K₂The total mass ratio of O is (0.22 to0.48)∶1。

Referring to fig. 2, a method for manufacturing a strengthened glass according to an embodiment of the present invention is a method for manufacturing a strengthened glass, and specifically includes the following steps:

step S210: the lithium zirconium aluminosilicate glass is treated with NaNO at the temperature of 390-420 ℃ and the mass ratio of 2: 8-8: 2₃And KNO₃The mixed molten liquid is toughened for 2 to 6 hours.

Specifically, the lithium zirconium aluminosilicate glass is the lithium zirconium aluminosilicate glass of the above embodiment. Specifically, the lithium zirconium aluminosilicate glass includes, by mass percent: SiO 2₂ 50％～72％，Al₂O₃ 10％～27％，B₂O₃0.1％～10.0％，Li₂O 2％～10％，Na₂O 4％～15％，ZrO₂0.1% -5.0% and K₂0 to 4% of O, wherein Li₂O、Na₂O and K₂O is 9% or more in total, ZrO₂And Al₂O₃Is greater than 10% by mass, and Li₂Mass of O and Li₂O、Na₂O and K₂The total mass ratio of the O to the N is (0.22-0.48) to 1.

Further, the mass ratio of the mixed melt in the step S210 is 6: 4 to 4: 6.

Step S220: then, the lithium zirconium aluminosilicate glass is treated with NaNO at the temperature of 380-400 ℃ and the mass ratio of 0.1: 99.9-15: 85₃And KNO₃The mixed molten liquid is toughened for 2 to 4 hours to obtain the strengthened glass.

The lithium zirconium aluminosilicate glass is strengthened by adopting a two-step salt mixing mode. The two-step salt mixing mode is adopted for strengthening the effects: ion species exchange is selectively carried out through a two-step chemical toughening method, the first step is mainly Li ions in glass and Na ions and K ions in toughening salts, Na-Li exchange can generate a compressive stress layer with a small compressive stress value and high stress depth, and a large stress is formed to make up for the problem of low stress value in the high depth direction along with partial Li-K and Na-K exchange; and secondly, tempering by using tempering salt with low temperature and high K ion content, rapidly exchanging Na ions in the glass and K ions in the tempering salt, forming a compact stress layer with low stress depth and high pressure stress value on the surface of the glass, and finally forming a composite stress layer, wherein the composite stress layer is mainly characterized in that the surface of the glass is provided with a high stress layer with the stress depth of more than 700MPa, and the depth direction of the stress layer is more than 100 mu m or even higher.

Wherein the mass ratio of the sodium nitrate to the potassium nitrate in the step S210 is set to be 2: 8-8: 2, and the effects are as follows: the chemical exchange between Na ions and Li ions in the glass is mainly realized to form a stress layer with enough depth, but the difference between the radiuses of the Na ions and the Li ions is not large, and enough space is formed in the glass structure to meet the conversion of the Na-Li ions, so that the depth of the formed stress layer is deep, but the stress value is low; the method is characterized in that the exchange of Li-K and Na-K is realized in the stress direction by adding K with large ionic radius into the toughened salt, and the partial compressive stress value is increased, so that the mass ratio of sodium nitrate to potassium nitrate in the first step is 2: 8-8: 2. In the step S220, the mass ratio of the sodium nitrate to the potassium nitrate is set to be 0.1: 99.9-15: 85, and the effects are as follows: mainly realizes the replacement of Na ions in the glass and K ions in toughened salt, thereby realizing a stress layer with a high compressive stress value on the surface of the glass, and forming a composite compressive stress layer with the first step of toughening, thereby increasing the strength and toughness of the glass.

In the two-step chemical tempering process, the temperature of the mixed melt in step S210 is generally 10 to 20 ℃ higher than that of the mixed melt in step S220. Because for two elements in the tempering process: temperature and time, the longer the same tempering salt treatment, the higher the temperature, the deeper the depth of the stress layer formed, however the stress value is significantly reduced. According to the purpose of the two-step toughening method of the invention, the first step is to form a stress layer with enough depth (more than 100 μm), and the second step is that the higher the stress value is, the better, so that the higher temperature is selected in the first step, generally 390-420 ℃, and the time is 2-6 hours. The second step is to form a high-stress layer (more than 700MPa) with a certain depth, so the second step needs a lower temperature, a shorter time, usually 380-400 ℃, for 2-4 hours, and the reasons of not selecting a long time are mainly that the tempering period is too long, the efficiency and the yield are low, the cost is high, and the mass production is not suitable.

The bending strength of the strengthened glass strengthened by the lithium zirconium aluminosilicate glass through the method is larger than 700MPa, the borne falling ball energy exceeds 0.4J, the situation that a screen or other cover glass of intelligent equipment such as a mobile phone is broken due to the fact that the intelligent equipment falls down to the ground carelessly can be effectively avoided or reduced, and therefore the strengthened glass can be used as protective glass for the mobile phone, a tablet personal computer or other mobile intelligent equipment.

A display device according to an embodiment includes the above lithium zirconium aluminosilicate glass, the above tempered glass, or a tempered glass produced by the above method for producing a tempered glass. The display device includes a smart mobile device, a digital camera, and the like. The lithium-zirconium aluminosilicate glass or the tempered glass has high strength, can be used as protective glass, and can avoid the situation that intelligent mobile equipment and the like are damaged due to careless falling.

The following are specific examples: