CN116081960A

CN116081960A - Chemically strengthened glass and glass device

Info

Publication number: CN116081960A
Application number: CN202111316090.1A
Authority: CN
Inventors: 覃文城; 袁小彬; 王刚刚; 吕路
Original assignee: Chongqing Aureavia Hi Tech Glass Co Ltd
Current assignee: Chongqing Aureavia Hi Tech Glass Co Ltd
Priority date: 2021-11-08
Filing date: 2021-11-08
Publication date: 2023-05-09

Abstract

The application discloses chemically strengthened glass and glass device, chemically strengthened glass with high tensile stress storage capacity and high bifurcation threshold, CT-LD of chemically strengthened glass _max More than 55000MPa/mm, CT-LD _max Maximum tensile stress linear density of plain glass which can be achieved by ion exchange under the condition that salt bath is 100wt% sodium nitrate melt and the temperature is 430 ℃; the bifurcation threshold value of the chemically strengthened glass is more than or equal to 43000MPa/mm, and the surface compressive stress CS of the chemically strengthened glass _max CS greater than 1180MPa _max Maximum compressive stress that can be achieved by ion exchange of plain glass in a salt bath of 100wt% potassium nitrate melt at a temperature of 430 ℃. In this way, the present application enables chemically strengthened glass to have high stress storage and high bifurcation threshold while having a high Young's modulus.

Description

Chemically strengthened glass and glass device

Technical Field

The application relates to the technical field of glass, in particular to chemically strengthened glass and a glass device.

Background

At present, the display protection materials and appearance shell protection materials of portable intelligent electronic devices such as mobile phones, flat plates and electronic watches are generally glass, and the glass is ultra-thin glass with the thickness of 0.5-0.8mm for ensuring the attractive appearance and strength. But the drop resistance of the current ultra-thin glass is low.

The chemically strengthened glass is produced by using high temperature ion exchange process to replace small alkali metal ion in glass with large alkali metal ion in high temperature molten salt to produce ion exchange volume difference, and to produce high to low pressure stress on certain surface layer of glass to block and delay the expansion of micro crack of glass and to raise the mechanical strength of glass.

Currently common chemically strengthened glasses include lithium aluminum silicon chemically strengthened glasses, which are developed in a direction to increase the deep compressive stress that the glass can accommodate, to obtain higher compressive stress during chemical strengthening to ensure high drop resistance. However, the glass itself has a limited structure and cannot safely accommodate high stress, and the stress exceeding the safety threshold can cause the glass to branch into small fragments after breaking according to the stress. Therefore, the requirements of the mobile phone terminal cannot be met, and the mobile phone terminal has bad influence on a user, so that in general production, the intelligent terminals such as mobile phones and the like can limit the safety threshold of the glass, the stress of which cannot be ultrahigh, and the existing glass has great waste in stress storage performance. Furthermore, the stress performance of the mobile phone is not only to be seen as the stress accommodating performance, but also to be seen as the glass network structure, and the stress degree can be safely accommodated, which is the key for determining the stress performance and the strength performance of the glass.

At present, the strength requirements of mobile phone terminals and customers on screen protection glass and cover plate protection glass are endless, for example, at present, an ultra-porcelain crystal panel, namely a microcrystalline glass panel, is introduced by apple 12, the drop resistance of the ultra-porcelain crystal panel is greatly improved, but the manufacturing cost is high, the ultra-porcelain crystal panel cannot be produced in a large scale, and the ultra-porcelain crystal panel can only be used for high-end flagship series in small batches. While the wider market still requires high performance lithium aluminum silicon glass to replace. And the lithium aluminum silicon glass is further developed to improve the anti-falling performance of the lithium aluminum silicon glass, and the capacity of accommodating stress and the safety threshold value are required to be synchronously improved.

Disclosure of Invention

The technical problem to be solved mainly by the application is to provide chemically strengthened glass and a glass device, which can enable the chemically strengthened glass to have high stress storage capacity and high bifurcation threshold value and high Young modulus.

In order to solve the technical problems, one technical proposal adopted by the application is that: provides a chemically strengthened glass with high tensile stress storage capacity and high bifurcation threshold, wherein the chemically strengthened glass is obtained by ion exchange of plain glass, and CT-LD of the chemically strengthened glass _max More than 55000MPa/mm, preferably more than 60000MPa/mm, CT-LD _max Maximum tensile stress linear density of plain glass which can be achieved by ion exchange under the condition that salt bath is 100wt% sodium nitrate melt and the temperature is 430 ℃; the bifurcation threshold value of the chemically strengthened glass is more than or equal to 43000MPa/mm, preferably more than or equal to 45000MPa/mm; surface compressive stress CS of chemically strengthened glass _max CS greater than 1180MPa _max Maximum compressive stress that can be achieved by ion exchange of plain glass in a salt bath of 100wt% potassium nitrate melt at a temperature of 430 ℃.

Wherein the glass is chemically strengthened ¹ DOL-0 is greater than or equal to 11% of the thickness of the plain glass, ¹ DOL-0 is the depth of compressive stress achieved by ion exchange of plain glass in a salt bath of 100wt% sodium nitrate melt at 430℃for 1 hour.

Wherein the CT-AV of the chemically strengthened glass is more than or equal to 86MPa.

Wherein the thickness of the chemically strengthened glass is 0.3-5mm.

Wherein the chemically strengthened glass is prepared from plain glass with atomic stacking density of more than or equal to 0.56 and less than or equal to 0.60 through ion exchange.

Wherein the sand-surface impact strength of the chemically strengthened glass is more than or equal to 1.6m.

The chemically strengthened glass comprises a strengthening layer positioned on the surface and a core layer positioned inside, and the composition of the core layer glass is the same as that of plain glass.

Wherein the plain glass comprises SiO ₂ 、Al ₂ O ₃ 、Y ₂ O ₃ And an alkali metal oxide, in mole fraction of oxide: [ Al ₂ O ₃ ]And [ SiO ] ₂ ]The total amount of (2) being 75mol% or more; [ SiO ] ₂ ]/([SiO ₂ ]+[Al ₂ O ₃ ]) Greater than 0.78, preferably greater than 0.80; (3 x [ Y ] ₂ O ₃ ]+[Al ₂ O ₃ ])/[SiO ₂ ]Greater than 0.16 and less than 0.45, preferably greater than 0.23 and less than 0.42; the total amount of alkali metal oxide is 16mol% or less, preferably 10 to 16mol%, more preferably 11 to 14mol%;

The alkali metal oxide includes Li ₂ O, and [ Li ] ₂ O]*(3*[Y ₂ O ₃ ]+[Al ₂ O ₃ ])/[SiO ₂ ]Greater than 2 and less than 4; wherein [ SiO ] ₂ ]、[Al ₂ O ₃ ]、[Y ₂ O ₃ ]、[Li ₂ O]The mole fraction of each component.

Wherein the basic oxide in the plain glass also comprises Na ₂ O，[Li ₂ O]/[Na ₂ O]Greater than 1 and less than 6, [ Na ] ₂ O]Is Na (Na) ₂ Mole fraction of O.

Wherein the plain glass further comprises MgO, [ MgO ]]/[Li ₂ O]Greater than 0.20 and less than or equal to 0.58, preferably greater than 0.23 and less than 0.52, more preferably greater than 0.22 and less than 0.45, [ MgO ]]Is the mole fraction of MgO.

Wherein, plain glass includes:

SiO ₂ ：59-72mol％、Al ₂ O ₃ ：8-16mol％、Y ₂ O ₃ ：1-10mol％、Li ₂ O：7-13mol％。

wherein the plain glass also comprises 1-7mol% of Na ₂ O, 0-3mol% of K ₂ O。

Wherein the plain glass further comprises 1.5-7mol% MgO, 0-5mol% B ₂ O ₃ Plain glass does not include P ₂ O ₅ And ZnO.

Wherein SiO in plain glass ₂ The molar fraction of (2) is 60 to 72mol%, preferably 65 to 72mol%; and/or

Al in plain glass ₂ O ₃ The molar fraction of (2) is 9 to 15mol%, preferably 9 to 13mol%; and/or

Y in plain glass ₂ O ₃ The molar fraction of (2) is 1 to 8mol%, preferably 1.5 to 6mol%, more preferably 5 to 6mol%; and/or

Li in plain glass ₂ The mole fraction of O is 8 to 12 mole%, preferably 8 to 10 mole%; and/or

Na in plain glass ₂ The mole fraction of O is 2 to 7mol%, preferably 2 to 5.5mol%; and/or

The mole fraction of MgO in the plain glass is 2 to 5.5 mole percent, preferably 2 to 4 mole percent; and/or

B in plain glass ₂ O ₃ The mole fraction of (2) is 0 to 2mol%; and/or

K in plain glass ₂ The mole fraction of O is 0 to 1 mole percent.

Wherein the atomic bulk density of the plain glass is greater than or equal to 0.56 and less than or equal to 0.60;

preferably, the elemental glass has an atomic bulk density greater than or equal to 0.58 and less than or equal to 0.60.

Wherein the bifurcation threshold of the plain glass is greater than 40000MPa/mm, preferably greater than 43000MPa/mm, more preferably greater than or equal to 45000MPa/mm.

Wherein the Young's modulus of the plain glass is 82GPa or more, preferably 88GPa or more.

Wherein the upper limit temperature of crystallization of the plain glass is not more than 1250 ℃.

Wherein the plain glass further comprises a clarifying agent with the content of not more than 1mol%, and the clarifying agent comprises one or two of tin oxide and sodium chloride.

In order to solve the technical problems, another technical scheme adopted by the application is as follows: there is provided a glass device made of the chemically strengthened glass of any one of the above.

The application also discloses a consumer electronics terminal comprising:

a housing including a front surface, a rear surface, and side surfaces;

and an electronic component partially within the housing, the electronic component comprising a display device located at or adjacent a front surface of the housing;

The front or/and rear or/and side surfaces comprise chemically strengthened glass having a high tensile stress storage and a high bifurcation threshold.

The consumer electronic terminal disclosed herein further comprises a cover article covering at the front surface of the housing or on the display device, the cover article comprising a chemically strengthened glass having a high tensile stress storage capacity and a high bifurcation threshold.

The consumer electronic terminal disclosed by the application comprises a mobile phone, a tablet personal computer or other electronic terminals (such as portable intelligent electronic devices like electronic watches).

The beneficial effects of this application are: unlike the prior art, the present application provides a chemically strengthened glass, and in particular, a CT-LD of the chemically strengthened glass, having a high tensile stress storage capacity and a high bifurcation threshold _max More than 55000MPa/mm, a bifurcation threshold value of more than or equal to 43000MPa/mm, and a surface compressive stress CS _max Above 1180MPa, the broken fragments can be prevented from being forked, and the high-surface compressive stress CS is provided, so that the impact resistance and the anti-falling performance are higher.

The plain glass adopted by the chemically strengthened glass has a network structure with high atomic stacking density and high integrity, so that the atomic stacking density of the glass is not obviously reduced after the plain glass is subjected to heat treatment, the relaxation resistance of the glass network structure is improved, the ion exchange stress performance of the glass is improved, and the Vickers hardness, young modulus, anti-drop performance, bifurcation threshold value and the like of the glass are improved.

Drawings

FIG. 1 is a schematic illustration of a sand face impact strength test in an embodiment of the present application;

fig. 2 is a schematic view of glass breakage in an embodiment of the present application.

Detailed Description

In order to make the objects, technical solutions and effects of the present application clearer and more specific, the present application will be further described in detail below with reference to the accompanying drawings and examples.

The present application provides a chemically strengthened glass having high stress storage and a high bifurcation threshold, while having a high Young's modulus. The chemically strengthened glass is prepared from plain glass with atomic stacking density of more than or equal to 0.56 and less than or equal to 0.60 through ion exchange. Ultra-thin plain glass can be produced by overflow, float and calendaring methods.

The thickness of the chemically strengthened glass is between 0.3 and 5mm, the structure is compact, the safety threshold of the glass can be improved, the stress effect generated by unit ion exchange can be improved, fragments can be prevented from being forked after being broken, the chemically strengthened glass has high surface compressive stress CS, and the chemically strengthened glass has higher impact resistance and anti-falling performance.

The chemically strengthened glass is applicable to consumer electronic terminals comprising:

a housing including a front surface, a rear surface, and side surfaces;

The consumer electronic terminal of the present application further comprises a cover article covering at the front surface of the housing or on the display, the cover article comprising a chemically strengthened glass having a high tensile stress storage capacity and a high bifurcation threshold.

The consumer electronic terminal comprises a mobile phone, a tablet computer or other electronic terminals (such as portable intelligent electronic devices like electronic watches). The chemically strengthened glass with high tensile stress storage capacity and high bifurcation threshold value can be used as a display protection material and an appearance shell protection material of consumer electronic terminals including mobile phones, tablet computers or other electronic terminals (such as portable intelligent electronic devices like electronic watches).

In one embodiment, the plain glass for making the chemically strengthened glass comprises SiO ₂ 、Al ₂ O ₃ 、Y ₂ O ₃ And an alkali metal oxide, the elemental glass having an atomic bulk density of greater than or equal to 0.56 and less than or equal to 0.60; preferably, the elemental glass has an atomic bulk density of greater than or equal to 0.58 and less than or equal to 0.60.

Wherein SiO is ₂ And Al ₂ O ₃ Is a main component constituting a glass network structure. SiO (SiO) ₂ The acid resistance of the glass can be improved, and the occurrence of cracking when flaws (indentations) remain on the surface of the glass can be reduced. Al (Al) ₂ O ₃ The surface compressive stress (Compressive Stress, CS) during the chemical strengthening treatment can be increased. SiO (SiO) ₂ And Al ₂ O ₃ As a main component constituting the glass network structure, al ₂ O ₃ And SiO ₂ May be greater than or equal to 75 mole% and [ SiO ] ₂ ]/([SiO ₂ ]+[Al ₂ O ₃ ]) Greater than 0.78, preferably greater than 0.80, [ SiO ] ₂ ]、[Al ₂ O ₃ ]The mole fraction of each component. High network structure composition, in particular high SiO ₂ The content can increase the amount of bridging oxygen in the glass, effectively reduce the dielectric constant of the glass at present, improve the network structural strength of the glass and enable the glass to have a higher safety threshold. The high network structure strength is beneficial to reducing stress relaxation effect generated by glass in ion exchange, and reducing weakening effect of factors such as high temperature, long time and the like in ion exchange on deep stress in composite compressive stress, so that the glass can adopt lower alkali metal ions and low-content alkali metal components to perform high-temperature single binary ion exchange, and composite compressive stress with certain depth and high tensile stress linear density can be obtained. And the reduction of the content of alkali metal ions dissociated in the glass network is also beneficial to the reduction of the dielectric constant.

The network structure of the main body of the glass is still a tetrahedral structure formed by silicon and aluminum, and the network main body mainly and approximately determines the forming process and the network structure strength.

Wherein SiO is ₂ The amount of (C) added may be 59 to 72mol%, preferably 60 to 72mol%, more preferably 65 to 72mol%. For example, siO ₂ The content of (2) may be 59mol%, 61mol%, 62mol%, 64mol%, 65mol%, 67mol%, 69mol%, 70mol%, 72mol%, or the like, or any subset or combination of these values may be used.

Al ₂ O ₃ May be added in an amount of 8 to 16mol%, preferably9 to 15mol%, more preferably 9 to 13mol%. For example, al ₂ O ₃ The content of (2) may be 8mol%, 9mol%, 10mol%, 11mol%, 12mol%, 13mol%, 14mol%, 15mol%, 16mol%, or the like, or any subset or combination of these values may be used.

B ₂ O ₃ The glass can be used as a glass secondary network structure, the addition of the glass secondary network structure can promote the high-temperature melting of the glass, reduce the melting difficulty and ensure that a proper amount of B ₂ O ₃ The addition of (2) can increase the ion exchange rate of the glass, is beneficial to reducing the brittleness of the glass and improving the scratch resistance of the glass, but the addition of excessive boron can lead to weakening of the network structure. Thus, B is a material for imparting a high strength network structure and scratch resistance to glass ₂ O ₃ The amount of (C) added may be 0 to 5mol%, preferably 1 to 3mol%, more preferably 0 to 2mol%. For example, B ₂ O ₃ The content of (3) may be 0.11mol%, 0.25mol%, 0.38mol%, 0.64mol%, 0.83mol%, 1.08mol%, 1.21mol%, 1.44mol%, 1.73mol%, 1.87mol%, 2.21mol%, 2.45mol%, 2.76mol%, 2.95mol%, 3mol%, 3.28mol%, 3.52mol%, 3.65mol%, 3.84mol%, 4mol%, 4.38mol%, 4.77mol%, 5mol%, etc., or any subset or combination of these values.

Y ₂ O ₃ Is a rare metal oxide, by adding Y to the glass ₂ O ₃ ，Y ₂ O ₃ The glass network structure can be promoted to change in the glass, and the formed Si-O-Y bond enables the isolated island network structure in the glass to be reconnected, so that the glass structure is improved, and meanwhile, bridge oxygen in the glass is increased, and the stability of the glass network is increased. And due to Y ³⁺ The mass fraction of ions in each component of the glass provided by the scheme is larger, the radius is larger, the ions have high field intensity in a glass network, the aggregation effect on free alkali metal and alkaline earth metal in the glass network is realized, the tightening trend is realized on the network structure, the whole structure of the glass is compact in arrangement, the densification degree is high, and the atomic stacking density of the glass can be improved. Thus Y ₂ O ₃ Can also reduce the post-annealing of the glassThe degree of structure relaxation can also improve the Vickers hardness of glass and the scratch resistance.

In one embodiment, the relaxation resistance of the network structure of the glass can be controlled by controlling the mole fractions of silica, alumina and yttria. Specifically, the first component ratio coefficient of the control glass is greater than or equal to 0.16 and less than 0.45, preferably greater than 0.23 and less than 0.42, and is (3 x [ Y) ₂ O ₃ ]+[Al ₂ O ₃ ])/[SiO ₂ ]，[SiO ₂ ]Is the mole fraction of silicon dioxide, [ Al ] ₂ O ₃ ]Is the mole fraction of aluminum oxide, [ Y ] ₂ O ₃ ]Is the mole fraction of yttrium oxide. By controlling the first component ratio coefficient to be greater than or equal to 0.16 and less than 0.45, the relaxation resistance of the network structure of the glass can be improved.

By adding Y to the glass ₂ O ₃ Although the structure of the glass can be made closer, Y ₂ O ₃ The addition of (2) affects the ion exchange rate, on the one hand, decreases the potassium-sodium exchange rate, and on the other hand, increases the unit stress generated by sodium-lithium exchange, thereby increasing the surface Compressive Stress (CS) of the tempered glass. Thus, in design Y ₂ O ₃ In addition to the relaxation resistance of the glass, the ion exchange capacity of the glass needs to be considered. On the basis, the ion exchange stress performance (comprising potassium-sodium and sodium-lithium ion exchange speed of the reinforced glass, unit stress effect generated by sodium-lithium ion exchange, maximum achievable CT-LD of the reinforced glass, maximum safely contained stress, relaxation sensitivity of the reinforced glass stress to temperature and the like) of the glass can be regulated by regulating the mole fraction of silicon dioxide, aluminum oxide, yttrium oxide and alkali metal oxides (such as lithium oxide, potassium oxide and sodium oxide).

In one embodiment, the control glass has a third component specific gravity of 2 or more and less than 4, the third component specific gravity being [ Li ] ₂ O]*(3*[Y ₂ O ₃ ]+[Al ₂ O ₃ ])/[SiO ₂ ]，[Li ₂ O]Is the mole fraction of lithium oxide. The ion exchange stress performance of the glass can be improved by adjusting the third component composition ratio to be more than or equal to 2 and less than 4.

At the time of adding Y ₂ O ₃ When the first component distribution ratio coefficient and the third component distribution ratio coefficient should be considered at the same time. Preferably Y ₂ O ₃ The addition amount of (c) can satisfy both the first component distribution ratio coefficient and the third component distribution ratio coefficient. Of course, if one wants to significantly optimize a certain property of the glass, Y ₂ O ₃ The addition amount of (2) can also only meet one component proportion coefficient to make the component proportion coefficient more biased towards the performance to be optimized, such as Y ₂ O ₃ The added amount of (c) preferably satisfies the first component ratio coefficient.

In one embodiment, Y ₂ O ₃ The content of (C) may be 1 to 10mol%, preferably 1 to 8mol%, more preferably 1.5 to 6mol%, still more preferably 2.5 to 5mol% or 5 to 6mol%. For example, Y ₂ O ₃ The content of (c) may be 1mol%, 1.3mol%, 2mol%, 2.45mol%, 3mol%, 3.65mol%, 4mol%, 4.55mol%, 5mol%, 5.5mol%, 6mol%, 6.5mol%, 7mol%, 7.5mol%, 8mol%, 8.5mol%, 9mol%, 9.5mol%, 10mol%, etc., or any subset or combination of these values may be used.

In other embodiments, lanthanum oxide (La ₂ O ₃ ) Thulium oxide (Tm) ₂ O ₃ ) Equal to Y ₂ O ₃ Rare earth metal oxide substitution Y with similar properties ₂ O ₃ . La can be added simultaneously ₂ O ₃ And Y ₂ O ₃ ，La ₂ O ₃ And Y ₂ O ₃ The total content of (2) is 2.5 to 6mol%, for example, 2.5mol%, 3mol%, 3.65mol%, 4mol%, 4.55mol%, 5mol%, 6mol%, etc., and any subset or combination of these values is also possible.

Na ₂ O、Li ₂ O、K ₂ O is the main component of ion exchange, na ion is the key exchange ion forming high surface compression stress, li ion is the key exchange ion forming deep compression stress, K ₂ O can effectively regulate the dielectric constant of the glass.

Due to Na ₂ O、Li ₂ O is alkali metal oxide, which is in a free state in the glass, and redundant oxygen ions break bridge oxygen to break up a network structure, so that the dielectric constant of the glass is increased, and excessive alkali metal elements increase the dielectric loss of the glass. Since the touchability of the cover glass requires that its dielectric constant not be too low, and that of 5G communications, K can be used ₂ O adjusts the dielectric constant of the glass, the radius of K ions is maximum, the K ions are not easy to accumulate, and the small addition does not affect the potassium-sodium and sodium-lithium ion exchange.

In one embodiment, the glass has good ion exchange stress properties and a suitable dielectric constant. The second component ratio of the glass can be controlled to be 16mol% or less, preferably 10 to 16mol%, more preferably 11 to 14mol%. The second component has a specific coefficient of [ Na ] ₂ O]+[K ₂ O]+[Li ₂ O]，[Na ₂ O]Is mole fraction of sodium oxide, [ K ] ₂ O]Mole fraction of potassium oxide, [ Li ] ₂ O]Is the mole fraction of lithium oxide. The second component ratio is preferably 14mol% or less, and may be, for example, 13mol%, 12.5mol%, 11mol%, or the like, or any subset or combination of these values.

In one embodiment, in order to provide the glass with better ion exchange stress performance, the fourth component specific gravity of the glass is more than or equal to 1 and less than 6, and is [ Li ] ₂ O]/[Na ₂ O]. Due to Li ₂ O is a main component of lithium aluminum silicon crystallization, and excessive O can raise the upper crystallization limit of glass, which causes production difficulty. While Na is ₂ The increase in O, while increasing CS, impedes sodium-lithium exchange, thereby reducing the deep stress CT-Ldmax. The alkali metal needs to control its total amount and Li ₂ O and Na ₂ O ratio.

After adding Na ₂ O、Li ₂ O、K ₂ At the time of O, the second component distribution ratio coefficient, the third component distribution ratio coefficient, and the fourth component distribution ratio coefficient should be considered at the same time. Preferably Na ₂ O、Li ₂ O、K ₂ The addition amount of O canAnd simultaneously satisfies the second component distribution ratio coefficient, the third component distribution ratio coefficient, and the fourth component distribution ratio coefficient. Of course, if one wants to significantly optimize a certain property of the glass, na ₂ O、Li ₂ O、K ₂ The addition amount of O can also only meet the proportion coefficient of one component, so that the performance to be optimized is more biased, such as Na ₂ O、Li ₂ O、K ₂ The addition amount of O preferentially satisfies the second component ratio coefficient.

In one embodiment, na ₂ The O content may be 1 to 7mol%; preferably 2 to 7mol%, more preferably 2 to 5.5mol%, and also preferably 1.5 to 4mol%, for example, na ₂ The content of O may be 1mol%, 1.25mol%, 1.38mol%, 1.46mol%, 1.64mol%, 1.75mol%, 1.83mol%, 1.95mol%, 2.08mol%, 2.21mol%, 2.45mol%, 2.76mol%, 2.95mol%, 3mol%, 3.28mol%, 3.52mol%, 3.65mol%, 3.84mol%, 4mol%, 4.38mol%, 4.77mol%, 5.11mol%, 5.62mol%, 6mol%, 6.26mol%, 6.57mol%, 7mol%, etc., or any subset or combination of these values.

Li ₂ The O content may be 7 to 13mol%, preferably 8 to 12mol%; more preferably 8 to 10mol%, still more preferably 7.5 to 10mol%, for example, li ₂ The content of O may be 7mol%, 7.25mol%, 7.41mol%, 7.5mol%, 7.63mol%, 7.81mol%, 7.95mol%, 8.06mol%, 8.24mol%, 8.41mol%, 8.67mol%, 8.89mol%, 9mol%, 9.29mol%, 9.51mol%, 9.68mol%, 9.87mol%, 10.0mol%, 10.44mol%, 10.92mol%, 11.37mol%, 11.63mol%, 12.0mol%, 12.63mol%, 13.0mol%, etc., or any subset or combination of these values.

K ₂ The O content may be 0 to 3mol%, preferably 0 to 1mol%, for example, K ₂ The content of O may be 0.13mol%, 0.37mol%, 0.48mol%, 0.66mol%, 0.89mol%, 1.05mol%, 1.36mol%, 1.61mol%, 1.99mol%, 2.24mol%, 2.55mol%, 2.73mol%, 3mol%, or the like, or any subset or combination of these values.

Due to Na ₂ O、Li ₂ O is an alkali metal oxide, whichThe glass is in a free state, redundant oxygen ions of the glass break bridge oxygen, break a network structure, reduce the intrinsic strength, enable the glass to be easier to stress and relax, lead to the rise of the dielectric constant of the glass, and lead the dielectric loss of the glass to be increased by excessive alkali metal elements, so that Na can be controlled ₂ O and Li ₂ The total content of O can lead the glass to have better ion exchange stress performance. Na (Na) ₂ O+Li ₂ The content of O may be 11mol%, 11.11mol%, 11.48mol%, 11.75mol%, 11.97mol%, 12.23mol%, 12.59mol%, 12.77mol%, 13mol%, 13.5mol%, 14mol%, 14.5mol%, 15mol%, 16mol%, or the like, or any subset or combination of these values may be used.

The plain glass may also include magnesium oxide (MgO), which may be present in the glass as a network intermediate, which has the effect of reducing the high temperature viscosity of the glass and increasing the Young's modulus of the glass. However, alkaline earth metals and alkali metals are the main carriers of current in glass, too much introduction can greatly improve the dielectric constant and dielectric loss of the glass, and the introduction of different alkali metals and alkaline earth metals can also produce mixed alkali or alkaline earth effects, which deteriorate the dielectric properties of the glass. In addition, since the radius of magnesium ions is 0.072nm, the accumulation of small ions hinders potassium-sodium and sodium-lithium ion exchange (lithium ions 0.076nm, sodium ions 1.02nm and potassium ions 1.38 nm), and particularly, the radius of magnesium ions is similar to that of lithium ions, and the inhibition on sodium-lithium ion exchange is obvious.

In one embodiment, to provide a glass with better ion exchange stress properties and a high Young's modulus, the fifth component ratio of the glass may be controlled to be greater than 0.20 and less than or equal to 0.58, preferably greater than 0.23 and less than 0.52, more preferably greater than 0.22 and less than 0.45, with the fifth component ratio being [ MgO ]]/[Li ₂ O]，[MgO]Is the mole fraction of magnesium oxide, [ Li ] ₂ O]Is the mole fraction of lithium oxide. Preferably, the fifth component partition ratio coefficient is less than 0.25.

In one embodiment, the MgO content may be 1.5 to 7mol%, preferably 2 to 5.5mol%; more preferably 2 to 4mol%, still more preferably 2 to 3mol%, for example, the MgO content may be 1.5mol%, 2mol%, 2.21mol%, 2.45mol%, 2.76mol%, 2.95mol%, 3mol%, 3.28mol%, 3.52mol%, 3.65mol%, 3.84mol%, 4mol%, 4.38mol%, 4.77mol%, 5mol%, 5.5mol%, etc., and any subset or combination of these values may be used.

Above, the plain glass provided by the present application is prepared by adjusting the ratio of each component, in particular [ Al ] ₂ O ₃ ]And [ SiO ] ₂ ]The total amount of (2) being greater than or equal to 75 mole%; [ SiO ] ₂ ]/([SiO ₂ ]+[Al ₂ O ₃ ]) Greater than 0.78, preferably greater than 0.80; (3 x [ Y ] ₂ O ₃ ]+[Al ₂ O ₃ ])/[SiO ₂ ]Greater than 0.16 and less than 0.45, preferably greater than 0.23 and less than 0.42; [ Li ] ₂ O]*(3*[Y ₂ O ₃ ]+[Al ₂ O ₃ ])/[SiO ₂ ]Greater than 2 and less than 4; the total amount of alkali metal oxide is 16mol% or less, preferably 10 to 16mol%, more preferably 11 to 14mol%. The plain glass can have a network structure with high atomic stacking density and high integrity. So that the atomic bulk density of the plain glass is greater than or equal to 0.56 and less than or equal to 0.60; preferably, the elemental glass has an atomic bulk density greater than or equal to 0.58 and less than or equal to 0.60. Meanwhile, the Young's modulus of the plain glass is more than or equal to 82GPa, preferably more than or equal to 88GPa. The network structure strength of the glass can be improved, the high network structure strength is beneficial to reducing the stress relaxation effect of the glass in ion exchange, reducing the weakening effect of factors such as high temperature and long time in ion exchange on deep stress in composite compressive stress, and the bifurcation threshold of the glass can be more than 40000MPa/mm, preferably more than 43000MPa/mm, more preferably more than or equal to 45000MPa/mm. When the tensile stress linear density CT-LD of the glass exceeds the bifurcation threshold value, breakage cracks generated during breakage of the glass can be bifurcated in the extending process, and a lot of fine fragments are generated after breakage.

In one embodiment, the plain glass comprises, in mole fractions: 59-72mol% of silicon dioxide (SiO ₂ ) 8-16mol% of aluminum oxide (Al ₂ O ₃ ) 0-5mol% of diboron trioxide (B) ₂ O ₃ ) 1.5 to 7mol% of magnesium oxide (MgO), 1-10mol% of yttrium oxide (Y) ₂ O ₃ ) 1-7mol% sodium oxide (Na ₂ O), 0-3mol% of potassium oxide (K) ₂ O) and 7-13mol% lithium oxide (Li) ₂ O), and does not include P ₂ O ₅ And ZnO; wherein [ Al ₂ O ₃ ]And [ SiO ] ₂ ]The total amount of (2) being greater than or equal to 75 mole%; [ SiO ] ₂ ]/([SiO ₂ ]+[Al ₂ O ₃ ]) Greater than 0.78;

(3*[Y ₂ O ₃ ]+[Al ₂ O ₃ ])/[SiO ₂ ]greater than 0.16 and less than 0.45;

[Li ₂ O]*(3*[Y ₂ O ₃ ]+[Al ₂ O ₃ ])/[SiO ₂ ]greater than 2 and less than 4;

the total amount of alkali metal oxides is less than or equal to 16mol%; [ Li ] ₂ O]/[Na ₂ O]Greater than 1 and less than 6; [ MgO (magnesium oxide)]/[Li ₂ O]Greater than 0.20 and less than or equal to 0.58.

Through regulating and controlling the values of all the components and ensuring that the proportioning relation among all the components is met, the plain glass can have a network structure with high atomic stacking density and high integrity, the network structure strength, young modulus, bifurcation threshold value and the like of the glass can be improved, the holding stress performance of the plain glass is further improved, the safety and the anti-drop performance of the glass are further improved, and the glass can be ensured to have better ion exchange stress performance (such as ensuring faster ion exchange speed and the like).

In one embodiment, the plain glass comprises, in mole fractions: 60-72mol% of silicon dioxide (SiO ₂ ) 9-15mol% of aluminum oxide (Al ₂ O ₃ ) 0-2mol% of diboron trioxide (B) ₂ O ₃ ) 2 to 5.5mol% of magnesium oxide (MgO), 1 to 8mol% of yttrium oxide (Y) ₂ O ₃ ) 2-7mol% sodium oxide (Na ₂ O), 0-1mol% of potassium oxide (K) ₂ O) and 8-12mol% lithium oxide (Li) ₂ O), and does not include P ₂ O ₅ And ZnO; [ Al ₂ O ₃ ]And [ SiO ] ₂ ]The total amount of (2) being greater than or equal to 75 mole%; [ SiO ] ₂ ]/([SiO ₂ ]+[Al ₂ O ₃ ]) Greater than0.80；

(3*[Y ₂ O ₃ ]+[Al ₂ O ₃ ])/[SiO ₂ ]Greater than 0.23 and less than 0.42;

the total amount of alkali metal oxide is 10 to 16mol%; [ Li ] ₂ O]/[Na ₂ O]Greater than 1 and less than 6;

[MgO]/[Li ₂ O]greater than 0.20 and less than or equal to 0.58.

In one embodiment, the plain glass comprises, in mole fractions: 65-71mol% of silicon dioxide (SiO ₂ ) 9-13mol% of aluminum oxide (Al ₂ O ₃ ) 0-2mol% of diboron trioxide (B) ₂ O ₃ ) 2 to 5.5mol% of magnesium oxide (MgO), 1.5 to 6mol% of yttrium oxide (Y) ₂ O ₃ ) 2-7mol% sodium oxide (Na ₂ O), 0-1mol% of potassium oxide (K) ₂ O) and 8-10mol% lithium oxide (Li) ₂ O), and does not include P ₂ O ₅ And ZnO; [ Al ₂ O ₃ ]And [ SiO ] ₂ ]The total amount of (2) being greater than or equal to 75 mole%; [ SiO ] ₂ ]/([SiO ₂ ]+[Al ₂ O ₃ ]) Greater than 0.80;

[MgO]/[Li ₂ O]greater than 0.20 and less than or equal to 0.58.

In one embodiment, the plain glass comprises, in mole fractions: 65-71mol% of silicon dioxide (SiO ₂ ) 9-13mol% of aluminum oxide (Al ₂ O ₃ ) 0-2mol% of diboron trioxide (B) ₂ O ₃ ) 2 to 5.5mol percent of magnesium oxide (MgO), 1.5 to 6mol percentYttria (Y) ₂ O ₃ ) 2-7mol% sodium oxide (Na ₂ O), 0-1mol% of potassium oxide (K) ₂ O) and 8-10mol% lithium oxide (Li) ₂ O), and does not include P ₂ O ₅ And ZnO; [ Al ₂ O ₃ ]And [ SiO ] ₂ ]The total amount of (2) being greater than or equal to 75 mole%; [ SiO ] ₂ ]/([SiO ₂ ]+[Al ₂ O ₃ ]) Greater than 0.83;

(3*[Y ₂ O ₃ ]+[Al ₂ O ₃ ])/[SiO ₂ ]greater than 0.23 and less than 0.41;

the total amount of alkali metal oxide is 11 to 14mol%; [ Li ] ₂ O]/[Na ₂ O]Greater than 1 and less than 6;

[MgO]/[Li ₂ O]greater than 0.23 and less than 0.52.

In one embodiment, the plain glass further includes a fining agent in an amount of no more than 1 mole percent, the fining agent including one or both of tin oxide and sodium chloride.

In one embodiment, the melting temperature of the resulting glass is between 1630 ℃ and 1700 ℃ and the upper crystallization limit temperature of the glass is not more than 1250 ℃. The temperature of the glass does not exceed 1500 ℃ when the viscosity of the glass is 2.7log pa and 1290 ℃ when the viscosity of the glass is 3.65log pa.

Specifically, the glass provided by the application is preferably produced by a float process, the specific flow of the float process is shown in fig. 1, the front part of the float process is a melting, clarifying and channel leaving part, the middle part of the float process is a tin bath forming device, and a roller way annealing device is arranged at the rear part of the float process.

An important forming section in the float process is the drawing and flattening of the glass melt gob on top of the molten tin by an edge roller. The melting point of tin is 231 ℃ and the boiling point is 2260 ℃, but in order to prevent the defects of volatilization and oxidation of tin liquid on glass, the maximum temperature of the front end of the tin liquid is 1250-1300 ℃ generally due to the limit of heat preservation materials of the milling groove heating materials, the temperature of the front end of the tin liquid is gradually reduced, and the tail end outlet is about 600-700 ℃. Therefore, when the float process is used to produce ultra-thin glass, the glass melt mass needs to have a specific viscosity after the channel falls into the tin surface, so that the glass melt mass spreads at a certain speed, and the glass melt mass can be slowly pulled by edge rollers at two sides to be spread and thinned. If the viscosity is too high, the edge roller cannot be effectively unfolded, and the edge roller cannot be easily pulled apart and cannot be molded. If the viscosity is too low, the adhesive can be spread out too early, the adhesive is easy to break in the middle when the edge is pulled, the thickness cannot be controlled, and the adhesive cannot be molded. It is therefore desirable to control specific viscosities and temperatures to meet the above-described requirements of the present application.

In the glass provided by the application, the viscosity can be kept in a proper range when the float process is carried out to prepare the ultrathin glass by effectively controlling the limitation of the network structure component and the alkali metal component in the material component.

In one embodiment, chemically strengthened glass may be prepared by increasing the strength of the glass by chemical strengthening. Specifically, the raw glass is immersed in a molten salt bath to perform ion exchange, and the composition of the surface of the glass after strengthening changes due to the ion exchange, but the composition of the core glass is consistent with that before the exchange. That is, the resulting chemically strengthened glass includes a strengthening layer on the surface and a core layer on the inside, the composition of the core layer glass being the same as that of the plain glass.

The plain glass provided by the application is prepared by controlling the second component ratio coefficient [ Na ] ₂ O]+[K ₂ O]+[Li ₂ O]10 to 16mol% of a third component composition ratio [ Li ] ₂ O]*(3*[Y ₂ O ₃ ]+[Al ₂ O ₃ ])/[SiO ₂ ]More than 2 and less than 4, and a fourth component composition ratio coefficient [ Li ] ₂ O]/[Na ₂ O]More than 1 and less than 6, and a fifth component composition ratio coefficient [ MgO ]]/[Li ₂ O]Greater than 0.20 and less than or equal to 0.58, can provide the glass with higher ion exchange properties, such as higher exchange efficiency and rate, and further increase the stress level of the glass.

Specifically, chemically strengthened glass can be obtained by immersing plain glass in a molten salt bath for ion exchange, and the mechanical properties of the obtained chemically strengthened glass are different under different ion exchange conditions.

The present application provides glass having a thickness of 0.7mm at 430 ℃ 100wt% nano ₃ * Sodium-lithium ion exchange under 1h conditions, and the stress depth obtained by the chemically strengthened glass obtained by the sodium-lithium ion exchange ¹ DOL-0 is greater than or equal to 11% of the glass thickness, and the surface compressive stress CS-50 (representing the compressive stress value at a depth of 50 microns down the glass surface) is greater than 90MPa.

Further, the highest compressive stress performance achieved when the glass is subjected to ion exchange can be detected, specifically, the glass can be subjected to strengthening experiments under the condition of 430 ℃ pure sodium salt (namely 100wt% sodium nitrate melt), test stress is taken out every 1h during the process, and the glass is placed into a salt bath to be subjected to ion exchange continuously after the test is finished until the tensile stress linear density CT-LD is at the highest point. Experiments have found that the highest CT-LD (i.e. CT-LD _max ) May be greater than 55000MPa/mm, preferably greater than 60000MPa/mm. The glass used in the experiment may be ultra-thin glass having a thickness of 0.7 mm.

Further, the chemically strengthened glass has a bifurcation threshold value of 43000MPa/mm or more, preferably 45000MPa/mm or more.

Further, the chemically strengthened glass of the present application has a surface compressive stress CS _max CS greater than 1180MPa _max Maximum compressive stress that can be achieved by ion exchange of plain glass in a salt bath of 100wt% potassium nitrate melt at a temperature of 430 ℃.

Further, the chemically strengthened glass of the present application has a thickness of 0.3 to 5mm.

Further, the chemically strengthened glass of the present application has a CT-AV of 86MPa or more.

Further, the chemically strengthened glass of the present application has a sand face impact strength of 1.6m or greater.

In an embodiment, the green glass may be subjected to a 3D hot bending process to form a curved structure. Specifically, the 3D hot bending process is to use a 3D hot bender to heat-bend glass to obtain curved glass in a 3D shape. The 3D hot bending machine adopts a DTK-DGP-3D12S3D model or similar hot bending machines of other companies, and is generally formed by adopting a graphite die, and the glass is formed by hot bending through heating and pressurizing the graphite die. The pressure of the 3D hot bending process is typically 0.1-2 atmospheres and the temperature is typically between the glass softening point minus 100-50 ℃. The heat bending temperature of the lithium aluminum silicon-based ultrathin glass on the market at present is between 650 and 750 ℃, after heating is carried out during the temperature period, the temperature is rapidly reduced (12 beats are generally carried out when the glass is subjected to 3D heat bending, each beat is 30 to 60 seconds, and only 3 beats are used for cooling, namely, in the heat bending, the glass can be reduced from 700 ℃ to about 30 ℃ in less than 3 minutes), the process can lead to the relaxation of a glass network structure, the non-rebound is compact, and the macroscopic appearance is that the bulk density is reduced. The relaxation of the glass network structure can lead to the reduction of compressive stress effect generated by ions exchanged in units, and finally can lead to the 2D glass and the thermally bent 3D glass with the same components, and under the same exchange process and the same exchange quantity, the stress of the 3D glass is smaller than that of the 2D glass, and finally, the strength performance, especially the anti-falling performance, is reduced, and the problems of unstable strengthening size and the like are also caused.

According to the plain glass provided by the application, the composition of the components in the plain glass is adjusted, the consumption of each oxide in the glass is controlled to meet a specific relational expression, the plain glass can have a network structure with high atomic stacking density and high integrity, the relaxation resistance of the glass can be improved, the glass can also have higher atomic stacking density after being subjected to 3D hot bending treatment, the reduction of the atomic stacking density of the glass after being subjected to 3D hot bending treatment is less than 0.003, and the atomic stacking density of the obtained 3D hot bending glass is greater than or equal to 0.56 and less than or equal to 0.60. That is, the same glass composition, the atomic packing density of both the glass in the 2D state and the glass in the 3D curved surface state is substantially the same, and the glass does not relax due to the 3D hot bending treatment.

In one embodiment, a strengthening experiment is performed on curved glass (namely, 3D hot-bent glass) obtained after the 3D hot-bending treatment, the strengthening experiment is performed on the 3D hot-bent glass under the condition of pure sodium salt at 430 ℃, test stress is taken out every 1h during the process, and the glass is placed into a salt bath to continue ion exchange after the test is completed until the highest point of the tensile stress linear density CT-LD appears.

The obtained 3D hot bending reinforcementThe glass also has higher stress level, and the CT-LD of the obtained hot-bending reinforced glass _max Is larger than 52000MPa/mm, CT-AV _max Is larger than 80MPa, CT-LD _max The maximum tensile stress linear density of glass can be achieved by ion exchange under the condition that the salt bath is 100wt% sodium nitrate melt and the temperature is 430 ℃; CT-AV _max The maximum average tensile stress that can be achieved by ion exchange of glass in a salt bath of 100wt% sodium nitrate melt at a temperature of 430 ℃. CT-LD of 3D hot-bent tempered glass relative to chemically-tempered glass obtained by ion exchange of non-hot-bent plain glass _max The drop amplitude is less than 3000MPa, and the maximum average tensile stress CT-AV is high _max The drop amplitude is less than 4MPa, preferably less than or equal to 3MPa.

In the above embodiment, in view of the fact that the existing ultrathin glass has a structure relaxation caused by rapid annealing in mass production and has lower stress than that in design, the application provides novel glass and chemically strengthened glass prepared from the glass, the glass has a network structure with high bulk density and high integrity, the relaxation degree of the network structure is small in the rapid annealing process, the high stress level can be obtained after 3D hot bending and strengthening, and the performance stability is ensured. The stress level of the chemically strengthened glass can be in the highest value state as far as possible, and the stress relaxation phenomenon brought by the chemically strengthened glass in the annealing thermal shock process is reduced.

In the above embodiments, the present application aims to further improve the stress accommodating performance and the bifurcation threshold capability of the plain glass, further improve the safety and the anti-drop performance of the glass, so as to meet the requirements of mobile phone terminals and consumers on strength, face the challenges of the microcrystalline glass with higher performance, develop the high CS characteristic of the dual-strength glass, and improve the competitiveness of the chemically strengthened glass and the microcrystalline glass. The glass is used for display protection and cover plate protection of high-end mobile phones, and is also used for display protection of watches and intelligent products.

The present application will be illustrated and explained by the following sets of specific embodiments, but should not be used to limit the scope of the present application.

Raw materials of the glass compositions of the respective examples were prepared, and glasses were prepared according to the formulations of the glass compositions of the examples, and the components and proportions of the obtained glasses are shown in Table 1. And performing various performance tests or treatments on the obtained glass, wherein the treatment method, the test method and the standard are as follows:

1. atomic packing density

The atomic bulk density is calculated by:

atomic packing density= (ρ/(M) _{Total (S)} /V _{Total (S)} )*100。

Wherein: ρ is the glass density in units of: g/cm3, and testing at 25 ℃ by adopting an Archimedes drainage method.

M _{Total (S)} ＝M _a +M _b +...；

Wherein: m is M _a 、M _b The molar mass of each oxide composition in the glass. For example, the mole fraction of oxide a in the glass is Mol _a Oxide relative molecular mass F _ma ，

M _a ＝Mol _a *F _ma 。

V _{Total (S)} ＝V _a +V _b +...；

Wherein: v (V) _a 、V _b Molar volume of each oxide composition of the glass. For example, the mole fraction of oxide a in the glass is Mol _a The oxide in the glass is X _ⅰ 、Y _ⅱ Its oxide molecular volume F _Va ＝(4*π/3)*NA*(ⅰ*r _x ³ +ⅱ*r _Y ³ )*10 ^-21 ，

V _a ＝Mol _a *F _va ，

NA is Avgalileo constant 6.02 x 10 ²³ ，r _x 、r _Y The ionic radii of the cations and anions in the oxide (the ionic radius here means the Bao Linli sub-radius) are respectively expressed in nm.

2. Young's modulus

Young's modulus is a physical quantity describing the ability of a solid material to resist deformation, as per GB/T7962.12-2010 colorless optical glass test method part 6: young's modulus, shear modulus, and Poisson's ratio.

3. Surface compressive stress CS and depth of compressive stress DOL

After the glass is chemically strengthened, the alkali metal ions with smaller radius on the surface are replaced by the alkali metal ions with larger radius, and the compressive stress is generated on the surface of the glass due to the crowding effect of the alkali metal ions with larger radius. The depth of compressive stress refers to the distance from the surface of the strengthened glass to the point where the compressive stress is zero.

Measurement of surface compressive stress and depth of compressive stress FSM6000 and SLP2000, manufactured by Orihara corporation, were measured for the surface high-pressure stress region and the deep low-pressure stress region, respectively, and the stress curves were fitted using PMC software. Of course, other stress testers that measure the high-pressure stress region and the low-pressure stress region may be used.

4. Average tensile stress CT-AV

Average tensile stress CT-AV: refers to the average value of the internal tensile stress of the glass after the glass is chemically strengthened, and is used for representing the stress degree of the chemically strengthened glass. Measured by SLP2000 manufactured by Orihara corporation.

5. Tensile stress linear density

Tensile stress linear density (Tensile stress linear density, CT-LD): the reinforced glass is placed in a salt bath for ion exchange to form a reinforced layer, a tensile stress layer is formed in the glass in the ion exchange process, the tensile stress layer is provided with an upper boundary which is separated from the upper surface of the reinforced glass by a certain distance and a lower boundary which is separated from the lower surface of the reinforced glass by a certain distance, the tensile stress of a line segment which is vertical to the upper boundary and the lower boundary at the same time in the tensile stress layer and is respectively located on the upper boundary and the lower boundary at the upper end point is a Y axis, a curve drawn by the X axis of the distance between the corresponding point and the upper boundary is recorded as a tensile stress curve, and the ratio of the fixed integral of the tensile stress curve and the reinforced thickness is recorded as the tensile stress linear density, namely the ratio of the sum of the tensile stress of the reinforced glass measured by an SLP-2000 stress instrument to the thickness of the glass.

6. Bifurcation threshold

The bifurcation threshold is the tensile stress linear density of the glass when the fracture surface of the glass is bifurcated in the glass immediate fracture experiment.

The immediate fracture test uses a "stress relief device" for the reinforced sample (please refer to the article "the inherent influence factor study on drop resistance of two-strength treated cover glass" from glass and enamel 2021,49 (02) ") to cause the fracture point to crack, the crack extends under the action of the internal tensile stress thereof, as shown in fig. 2a and fig. 2b, instead of the satellite explosion due to the excessive impact force, as shown in fig. 2c. When the glass crack just breaks off, the tensile stress linear density of the glass is the break off threshold.

7. Sand face impact resistance

Glass was prepared as (60-80) × (150-170) × 0.7mm samples. The load module is prepared from an acrylic plate and a metal load block, and glass is fixed on one surface of the load module in a foam and double-sided adhesive mode, and the concrete is shown in figure 1.

Wherein the weight of the load module acrylic plate and the iron block is 200g, and the thickness of the foam and the double-sided adhesive is 0.2-0.3mm. The prepared measurement sample is dropped from a prescribed height in a manner that the chemically strengthened glass is downward to a marble floor with 80-mesh sand paper attached, in an impact form, wherein the acceleration of impact drop is 9.5-9.8m/s ² . So as to simulate the state of carelessly falling when the mobile phone is normally used.

And (3) at least 10 samples in each batch are dropped from 0.4m, and the samples are subjected to one drop impact, if the samples are not broken, the height is increased by 0.1m each time, and the samples are dropped again until the samples are broken, and the secondary height of the broken height is the anti-drop height.

TABLE 1 content of glass component of examples and comparative examples

Table 2 glass performance parameters for examples, comparative examples

Note that: ¹ CT-LD _max is glass at 430 ℃ and 100wt% NaNO ₃ Maximum CT-LD which can be achieved by ion exchange under the condition; ² CT-LD _max the glass is heat treated for 1h under the condition of (strain point +200) DEG C, and then is heated at 430 ℃ and 100wt% NaNO ₃ Maximum CT-LD which can be achieved by ion exchange under the condition; CS (circuit switching) _max Glass at 430 ℃ and 100wt% KNO ₃ The maximum CS that can be achieved by ion exchange under conditions.

TABLE 3 glass performance parameters for examples and comparative examples

Note that: ³ the ratio coefficient is the third component ratio coefficient [ Li ] ₂ O]*(3*[Y ₂ O ₃ ]+[Al ₂ O ₃ ])/[SiO ₂ ]； ⁴ The ratio coefficient is a fourth component ratio coefficient [ Li ] ₂ O]/[Na ₂ O]； ⁵ The proportioning coefficient is the fifth ingredient proportioning coefficient [ MgO ]]/[Li ₂ O]； ¹ CT-LD _max Is glass at 430 ℃ and 100wt% NaNO ₃ Maximum CT-LD which can be achieved by ion exchange under the condition; ¹ DOL-0 is an ultra-thin glass with a thickness of 0.7mm at 430 ℃ and 100wt% NaNO ₃ The stress depth achieved by ion exchange was 1 h.

Table 4 glass performance parameters for each example, comparative example

Note that: CT-LD _max After the glass is heat treated for 4 hours at the corresponding temperature, the glass is treated with 100 weight percent of NaNO ₃ The maximum CT-LD that can be achieved by ion exchange under the condition.

TABLE 5 glass performance parameters for examples, comparative examples

	Treatment process	Atomic packing density	Young's modulus/GPa	CT-LD _max /MPa/mm	CT-AV _max /MPa
						Example 1	--	0.5721	98	59841	--
Example 1	Heat treatment of	0.5713	--	50251	--
						Example 5	--	0.5623	92	68500	102
Example 5	3D hot bending treatment	0.5601	91	66890	100
						Example 5	Heat treatment of	0.5616	--	63500	--
Example 6	--	0.5714	99	78562	115
						Example 6	3D hot bending treatment	0.5701	98	77650	112
Comparative example 1	--	0.5521	82	52321	75
						Comparative example 1	3D hot bending treatment	0.5450	76	46840	68
Comparative example 1	Heat treatment of	0.5477	--	38547	--

Note that: the heat treatment is that the glass is heat treated for 1h under the condition of (strain point +200); CT-LD _max Corresponding glass at 430 ℃ and 100wt% NaNO ₃ Maximum CT-LD which can be achieved by ion exchange under the condition; CT-AV _max Corresponding glass at 430 ℃ and 100wt% NaNO ₃ The maximum CT-AV that can be achieved by ion exchange under the condition.

TABLE 6 glass performance parameters for examples and comparative examples

TABLE 7 glass performance parameters for examples, comparative examples

The above examples, examples 1-7, add Y to the glass ₂ O ₃ And/or La ₂ O ₃ The atomic packing density is higher than that of the glass currently on the market, such as comparative example 1 and comparative example 2. The glass network structure is more complete and the arrangement is more compact due to the increase of the atomic packing density, and the Young's modulus of the glasses of examples 1-7 is greater than 88GPa, and some even exceeds 100GPa, relative to the comparative examples. Examples 5 and 6 are compared with comparative examples 1 and 2 in terms of stress properties such as CT-LD obtained by sodium-lithium exchange of glass with the same lithium content of glass _max Much higher than the comparative example; under the condition of compact structure, the stress obtained by the unit exchange amount is larger, the stress relaxation phenomenon degree in the ion exchange is lightened, and the high network compactness also brings higher bifurcation threshold value, so that the glass can safely contain higher stress, and the glass is ensured to have better anti-falling performance. High compactness can also obtain high surface CS, and can effectively improve the scratch resistance of the glass.

Since the atomic bulk density is not high, comparative example 1 requires a very high content of lithium to obtain CT-LD of more than 40000 MPa/mm. However, the structure is not compact, and the bifurcation threshold value is very low due to excessive addition of alkali metal, so that the high stress cannot be safely contained, and the cost of raw materials of the glass is increased due to the addition of wasted lithium.

Wherein, the [ Li ] of the glass of the present application ₂ O]*(3*[Y ₂ O ₃ ]+[Al ₂ O ₃ ])/[SiO ₂ ]The addition of the alumina is more than 2, the network structure can be more compact, the yttrium oxide high field strength substance can enable the glass structure to be more compact, the addition of the alumina and the yttrium oxide high field strength substance can synergistically improve the stress effect generated by unit ion exchange, the larger the proportion of the yttrium oxide and the silicon is relative to that of the silicon, the more the lithium oxide component is, the larger the stress effect generated by sodium-lithium exchange is, and the more the exchange quantity is. [ Li ] of the element glass of the present application ₂ O]/[Na ₂ O]Greater than 1 indicates that the lithium component of the glass is greater than the sodium component, and that excessive sodium component of the glass can result in sodium in the glass and the salt bathThe balance of the lithium exchange shifts towards the salt bath, reducing the amount of sodium-lithium exchange. And [ MgO ]]/[Li ₂ O]Less than or equal to 0.58, because the radius of magnesium ions is similar to that of lithium ions, excessive magnesium ions will block sodium-lithium exchange of lithium ions in glass, limiting [ MgO ] ]/[Li ₂ O]The switching speed can be ensured.

And it can be seen from the table that [ Li ] of the glass of the present application ₂ O]*(3*[Y ₂ O ₃ ]+[Al ₂ O ₃ ])/[SiO ₂ ]Greater than 2, [ Li ] ₂ O]/[Na ₂ O]A value greater than 1 ensures the stress effect and exchange amount generated, so that CT-LD thereof _max Are all more than 55000MPa/mm, and [ MgO ]]/[Li ₂ O]Less than or equal to 0.58, so that the exchange depth of the glass reaches more than 11% of the thickness of the glass in 100% sodium nitrate melt at 430 ℃ for 1 hour. And comparative example 3, which is [ MgO ]]/[Li ₂ O]Although less than or equal to 0.58, is not satisfied [ Li ] ₂ O]*(3*[Y ₂ O ₃ ]+[Al ₂ O ₃ ])/[SiO ₂ ]Greater than 2, [ Li ] ₂ O]/[Na ₂ O]Greater than 1, CT-LD thereof _max Lower than 50000MPa/mm. While comparative example 4 satisfies [ Li ] ₂ O]*(3*[Y ₂ O ₃ ]+[Al ₂ O ₃ ])/[SiO ₂ ]Greater than 2, [ Li ] ₂ O]/[Na ₂ O]Greater than 1, but because of [ MgO ]]/[Li ₂ O]And the depth of the sodium-lithium ion exchange reaches 0.8, and the sodium-lithium ion exchange is slow, and the exchange depth is only 9% of the thickness within 1 h.

Chemically strengthened glass is generally applied to cover plates, and the cover plate glass is often subjected to 3D hot bending treatment, and the temperature of the 3D hot bending treatment is generally about (strain point +200) °c. As can be seen in Table 4, the density of the glass structure decreases after the treatment at this temperature, which is evident as a decrease in physical density. Thereby affecting the stress performance degradation, e.g. CT-LD _max Eventually affecting the stress of the finished product, resulting in a decrease in drop resistance. In the application, the density of the obtained glass is higher, the descending amplitude of the density in the hot bending treatment is smaller and is basically less than 0.45 percent, and the stress influence is not great. Sample subjected to simulated 3D hot bending treatment and CT-LD _max Still greater than 50000MPa/mm or more, whereas the comparative example has a very large reduction.

According to Table 5, the sample of comparative example 1 was subjected to 3D heat bending treatment, and the bulk density and Young's modulus were significantly reduced as compared with those of examples 5 and 6 due to severe structural relaxation. Thereby causing CT-LD thereof _max And CT-AV _max Also drop too much, CT-Ld _max The drop is about 5000 MPa/mm. And compared with the stress of a conventional 2D glass sample and a sample subjected to 3D hot bending treatment, under the same strengthening process, the stress of the 3D sample of the comparative example 1 is reduced by 4000-5500MPa/mm, and the stress of the 3D sample of the examples 5 and 6 of the application is reduced by 800-2000MPa/mm only compared with that of the 2D sample, so that the effect is obvious.

According to tables 6-7, the stress after the glass reinforcement of the present application is substantially higher than that of the current products, the 2.5D drop height is greater than 1.5m, and the 3D sample is greater than 1.2m. Compared with the current sample, the anti-falling performance is greatly improved.

In the above embodiments, in view of the fact that the ultrathin glass is currently low in stress than the design due to the relaxation of the structure caused by rapid annealing in mass production. The application provides novel glass and chemically strengthened glass prepared from the glass, the glass has a network structure with high bulk density and high integrity, the relaxation degree of the network structure is small in the rapid annealing process, the high stress level can be obtained after 3D hot bending and strengthening, and the performance is ensured to be stable. The stress level of the chemically strengthened glass can be in the highest value state as far as possible, and the stress relaxation phenomenon brought by the chemically strengthened glass in the annealing thermal shock process is reduced.

From the above, it is clear that the ultra-thin tempered glass with a thickness of 0.7mm, which is made of the plain glass of the present invention, has a high stress storage capacity and a high bifurcation threshold, and at the same time has a high Young's modulus, can obtain a high stress level, and ensures stable performance. Of course, because the plain glass provided by the invention has a network structure with high atomic stacking density and high integrity, the relaxation degree of the network structure is small in the rapid annealing process, so that the chemically strengthened glass with the thickness of 0.3-5mm manufactured by adopting the plain glass can also obtain high stress level, and the performance stability is ensured.

The foregoing description is only of embodiments of the present application, and is not intended to limit the scope of the patent application, and all equivalent structures or equivalent processes using the descriptions and the contents of the present application or other related technical fields are included in the scope of the patent application.

Claims

1. A chemically strengthened glass having a high tensile stress storage capacity and a high bifurcation threshold, characterized by: the chemically strengthened glass is obtained by ion exchange of plain glass, and CT-LD of the chemically strengthened glass _max More than 55000MPa/mm, preferably more than 60000MPa/mm, CT-LD _max Maximum tensile stress linear density of plain glass which can be achieved by ion exchange under the condition that salt bath is 100wt% sodium nitrate melt and the temperature is 430 ℃;

the bifurcation threshold value of the chemically strengthened glass is more than or equal to 43000MPa/mm, preferably more than or equal to 45000MPa/mm;

surface compressive stress CS of the chemically strengthened glass _max CS greater than 1180MPa _max Maximum compressive stress that can be achieved by ion exchange of plain glass in a salt bath of 100wt% potassium nitrate melt at a temperature of 430 ℃.

2. A chemically strengthened glass according to claim 1, wherein: the chemically strengthened glass ¹ DOL-0 is greater than or equal to 11% of the thickness of the plain glass, ¹ DOL-0 is the depth of compressive stress achieved by ion exchange of plain glass in a salt bath of 100wt% sodium nitrate melt at 430℃for 1 hour.

3. A chemically strengthened glass according to claim 1, wherein: the CT-AV of the chemically strengthened glass is more than or equal to 86MPa.

4. A chemically strengthened glass according to claim 1, wherein: the thickness of the chemically strengthened glass is 0.3-5mm.

5. A chemically strengthened glass according to claim 1, wherein: the chemically strengthened glass is prepared from plain glass with atomic stacking density of more than or equal to 0.56 and less than or equal to 0.60 through ion exchange.

6. A chemically strengthened glass according to claim 1, wherein: the sand-surface impact strength of the chemically strengthened glass is more than or equal to 1.6m.

7. The chemically strengthened glass according to any one of claims 1 to 6 wherein:

the plain glass comprises SiO ₂ 、Al ₂ O ₃ 、Y ₂ O ₃ And an alkali metal oxide, in mole fraction of oxide:

[Al ₂ O ₃ ]and [ SiO ] ₂ ]The total amount of (2) being 75mol% or more;

[SiO ₂ ]/([SiO ₂ ]+[Al ₂ O ₃ ]) Greater than 0.78, preferably greater than 0.80;

(3*[Y ₂ O ₃ ]+[Al ₂ O ₃ ])/[SiO ₂ ]greater than 0.16 and less than 0.45, preferably greater than 0.23 and less than 0.42;

the total amount of alkali metal oxide is 16mol% or less, preferably 10 to 16mol%, more preferably 11 to 14mol%;

the alkali metal oxide comprises Li ₂ O, and [ Li ] ₂ O]*(3*[Y ₂ O ₃ ]+[Al ₂ O ₃ ])/[SiO ₂ ]Greater than 2 and less than 4;

wherein [ SiO ] ₂ ]、[Al ₂ O ₃ ]、[Y ₂ O ₃ ]、[Li ₂ O]The mole fraction of each component.

8. The chemically strengthened glass of claim 7 wherein: the basic oxide in the plain glass also comprises Na ₂ O，[Li ₂ O]/[Na ₂ O]Greater than 1 and less than 6, [Na ₂ O]Is Na (Na) ₂ Mole fraction of O.

9. The chemically strengthened glass of claim 7 wherein: the plain glass also comprises MgO, [ MgO ]]/[Li ₂ O]Greater than 0.20 and less than or equal to 0.58, preferably greater than 0.23 and less than 0.52, more preferably greater than 0.22 and less than 0.45, [ MgO ] ]Is the mole fraction of MgO.

10. The chemically strengthened glass of claim 7 wherein: the plain glass comprises:

SiO ₂ ：59-72mol％、

Al ₂ O ₃ ：8-16mol％、

Y ₂ O ₃ ：1-10mol％、

Li ₂ O：7-13mol％。

11. a chemically strengthened glass according to claim 10, wherein: the plain glass also comprises 1-7mol% of Na ₂ O, 0-3mol% of K ₂ O。

12. A chemically strengthened glass according to claim 10, wherein: the plain glass also comprises 1.5 to 7mol percent of MgO and 0 to 5mol percent of B ₂ O ₃ The plain glass does not include P ₂ O ₅ And ZnO.

13. A chemically strengthened glass according to claim 10, wherein: siO in the plain glass ₂ The molar fraction of (2) is 60 to 72mol%, preferably 65 to 72mol%; and/or

Al in the plain glass ₂ O ₃ The molar fraction of (2) is 9 to 15mol%, preferably 9 to 13mol%; and/or

Y in the plain glass ₂ O ₃ The molar fraction of (2) is 1 to 8mol%, preferably 1.5 to 6mol%, more preferably 5 to 6mol%; and/or

Li in the plain glass ₂ The mole fraction of O is 8-12 mol%,preferably 8 to 10mol%; and/or

Na in the plain glass ₂ The mole fraction of O is 2 to 7mol%, preferably 2 to 5.5mol%; and/or

B in the plain glass ₂ O ₃ The mole fraction of (2) is 0 to 2mol%; and/or

K in the plain glass ₂ The mole fraction of O is 0 to 1 mole percent.

14. A glass device, characterized by: the glass device made from the chemically strengthened glass of any one of claims 1-13.

15. A consumer electronic terminal comprising:

a housing including a front surface, a rear surface, and side surfaces;

the front surface or/and the rear surface or/and the side surface comprises the chemically strengthened glass having a high tensile stress storage capacity and a high bifurcation threshold as defined in any one of claims 1 to 13.

16. The consumer electronic terminal of claim 15 further comprising a cover article overlaying the front surface of the housing or the display device, the cover article comprising the chemically strengthened glass having a high tensile stress storage capacity and a high bifurcation threshold as recited in any one of claims 1-13.

17. A consumer electronic terminal as recited in claim 15 or 16, characterised in that the consumer electronic terminal comprises a cell phone, a tablet computer or other electronic terminal.