WO2020094028A1

WO2020094028A1 - Glass material, method of manufacturing glass material, and electronic apparatus

Info

Publication number: WO2020094028A1
Application number: PCT/CN2019/115839
Authority: WO
Inventors: 唐中帜; 欧阳辰鑫; 吕旺春
Original assignee: 华为技术有限公司
Priority date: 2018-11-08
Filing date: 2019-11-06
Publication date: 2020-05-14
Also published as: CN111153603B; CN111153603A

Abstract

Disclosed is a glass material, a method for manufacturing the glass material, and an electronic apparatus. The glass material contains crystals. A chemically strengthened layer of at least a partial region of one side of the glass material has a depth greater than 21% of a thickness thereof. The thickness is the distance between the surface of the one side of the glass material and a surface on the other side of the glass material, the one side being opposite to the other side. The glass material contains crystals capable of increasing the fracture toughness of the glass material. The glass material has a chemical strengthening layer with a large depth on one side, thereby improving the drop resistance of the glass material.

Description

Glass material, manufacturing method of glass material, electronic equipment

This application requires the application number 201811324229.5 filed on November 8, 2018, the invention name is "glass materials, methods of manufacturing glass materials, electronic equipment" and the application number filed on December 1, 2018 is 201811460627.X, The priority of the Chinese patent application titled "Glass Material, Manufacturing Method of Glass Material, Electronic Equipment", the entire content of which is incorporated by reference in this application.

Technical field

The present application relates to the field of materials, and more specifically, to glass materials, methods of manufacturing glass materials, and electronic devices.

Background technique

As consumers' requirements for the drop resistance of electronic devices such as mobile phones continue to increase, the cover glass used in mobile phones and other electronic products must have good drop resistance. In the past five to ten years, the cover glass of mobile phones and other electronic products has adopted the chemically strengthened glass as the mainstream trend, because after the glass is chemically strengthened, a certain depth of compressive stress layer is formed on the glass surface, thereby improving the strength and resistance to falling Sex.

However, according to the trend of ultra-thin glass cover sheets, the maximum chemical strengthening layer depth that can be obtained by the current mature chemical strengthening and physical strengthening process methods still cannot meet the strength requirements of ultra-thin glass cover sheets.

Therefore, how to increase the drop resistance of glass materials has become an urgent problem to be solved.

Summary of the invention

The present application provides a glass material, a manufacturing method of the glass material, and an electronic device, which can increase the depth of the chemical strengthening layer of the glass material, thereby improving the drop resistance of the glass material.

In a first aspect, the present application provides a glass material, the glass material containing crystals, at least a portion of the side of the glass material has a chemical strengthening layer depth greater than 21% of the thickness, the thickness being the surface of the glass material side and the glass The distance between the surfaces on the other side of the material, which is opposite to the other side.

In the above technical solution, the glass material contains crystals, which can increase the fracture toughness of the glass material, and the glass material has an ultra-deep chemical strengthening layer on one side, thereby improving the drop resistance of the glass material.

In a possible implementation manner, the crystal content of the glass material gradually decreases in a direction from at least a partial area of the starting side to at least a partial area of the ending side, the starting side is the one side and the other side The one with a higher crystal content in the middle, the end side is the one with a lower crystal content in the one side and the other side, and at least part of the area on the start side is opposite to at least part of the area on the end side.

In the above technical solution, the crystals contained in the glass material are unevenly distributed. Due to the different crystal content, the effect of ion exchange in chemical strengthening is different. In this way, at least part of the area on one side of the glass material and at least part of the area on the other side are subjected to symmetric or asymmetric chemical strengthening treatment. The deep chemical strengthening layer is deep in the glass material, thereby improving the drop resistance of the glass material.

In a possible implementation, the crystal content of the glass material gradually decreases to 95% or less of the crystal content of at least part of the starting side.

In the above technical solution, the crystal content on both sides of the glass material differs by at least 5%, which is easy to realize.

In a possible implementation, the crystal content of the glass material gradually decreases to 80% or less of the crystal content of at least part of the starting side.

In the above technical solution, the crystal content on both sides of the glass material differs by at least 20%, which is easy to realize.

In a possible implementation manner, the crystal content of the glass material gradually decreases to 50% or less of the crystal content of at least part of the starting side.

In the above technical solution, the crystal content on both sides of the glass material differs by at least 50%, which can make the effect of asymmetric chemical strengthening on both sides of the glass material more obvious.

In a possible implementation, the crystal content of the glass material gradually decreases to zero.

In a possible implementation manner, the crystal content of the glass material gradually decreases to 0 and keeps the crystal content at 0.

In a possible implementation, the depth of the chemical strengthening layer in at least part of the side is greater than 25% of the thickness. In the above technical solution, the glass material has an ultra-deep chemical strengthening layer on one side, which can improve the drop resistance of the glass material.

In a possible implementation manner, the depth of the chemical strengthening layer in at least a part of the side is greater than 21% of the thickness and less than or equal to 50% of the thickness. In the above technical solution, the glass material has an ultra-deep chemical strengthening layer on one side, which can improve the drop resistance of the glass material.

In a possible implementation manner, the depth of the chemical strengthening layer of at least a part of the side is greater than 21% of the thickness and less than or equal to 35% of the thickness. In the above technical solution, the glass material has an ultra-deep chemical strengthening layer on one side, which can improve the drop resistance of the glass material.

In a possible implementation manner, the depth of the chemical strengthening layer in at least part of the other side is smaller than the depth of the chemical strengthening layer in at least part of the side.

In a second aspect, the present application provides a method of manufacturing a glass material, the method comprising: crystallizing a glass substrate so that the glass substrate contains crystals; and further chemically strengthening the crystallized glass substrate To obtain a glass material with a depth of at least a part of the chemical strengthening layer on one side greater than 21% of the thickness, the thickness being the distance between the surface on one side and the surface on the other side of the crystallized glass substrate, so The one side is opposite to the other side.

In a possible implementation manner, the crystallizing the glass substrate includes: performing heat treatment based on a second temperature on at least a portion of the other side to crystallize at least a portion of the other side Change.

In the above technical solution, at least part of the region on the other side is crystallized. Since the effect of ion exchange in chemical strengthening is different between the glass phase and the crystal phase, at least part of one side and at least part of the other side Symmetrically chemically strengthened, the resulting glass-ceramic double-sided has a large surface compressive stress, and one side has an ultra-deep chemical strengthening layer depth, so it has better drop resistance.

In a possible implementation manner, the crystallizing the glass substrate, and the crystallizing the glass substrate further includes: performing heat treatment based on a second temperature on at least a portion of the one side, so that At least part of the region on one side is crystallized, and at least part of the region on the other side is opposite to at least part of the region on the one side.

In the above technical solution, the glass material contains crystals, which can increase the fracture toughness of the glass material, thereby improving the drop resistance of the glass material.

In a possible implementation manner, the first temperature is different from the second temperature.

In the above technical solution, at least part of one side of the glass material and at least part of the other side undergo heat treatment at different temperatures. Since the crystallization rate of the glass material is different at different temperatures, at least part of the crystal content on one side and at least part of the crystal content on the other side will be different, thereby obtaining a non-uniformly crystallized glass material. Further, at least part of one side and at least part of the other side are chemically strengthened. In glass materials with different crystal phase contents, the effect of ion exchange in chemical strengthening is different, so that at least part of one side and at least part of the other side can be asymmetrically chemically strengthened. Such a glass-ceramic double-sided has a large surface compressive stress, and one side has an ultra-deep chemical strengthening layer depth, so it has better drop resistance.

In a possible implementation manner, the one side is the one side; before chemically strengthening the crystallized glass substrate, the method further includes: coating at least a portion of the other side Chemical strengthening and restraining materials.

In the above technical solution, by suppressing the progress of chemical strengthening, the difference between the degree of chemical strengthening of at least one part of one side of the glass material and the at least part of the other side of the glass material is enlarged, and at least part of the glass material on the other side and at least the other side of the glass material are enlarged. The difference in the depth of the partial chemical strengthening layer makes the depth of the chemical strengthening layer on one side greater, further improving the drop resistance of the glass material.

In a possible implementation, the chemical strengthening suppression material is a high-temperature ink containing silicon oxide particles.

In a possible implementation manner, the chemical strengthening treatment of at least a part of the area on the one side and at least a part of the area on the other side includes: melting at least a part of the area on the one side based on the first concentration Chemical strengthening treatment of salt; at least a part of the other side is subjected to a chemical strengthening treatment based on a molten salt of a second concentration, the second concentration being different from the first concentration.

In the above technical solution, the two surfaces of the glass material are in contact with molten salts of different concentrations. Since the chemical strengthening is easier in molten salt with a higher concentration, this can further expand the difference between the degree of chemical strengthening of at least part of one side of the glass material and at least part of the other side of the glass material, thereby expanding at least one side of the glass material The difference in the depth of the chemical strengthening layer between at least part of the part and the other side makes the depth of the chemical strengthening layer on one side greater, further improving the drop resistance of the glass material.

In a possible implementation, when the first temperature is lower than the second temperature, the first temperature is the temperature after at least a part of the other side of the glass material is cooled by contacting the cooling plate, or when the first temperature When a temperature is higher than the second temperature, the second temperature is a temperature after at least a part of the glass material side is cooled by contacting the cooling plate.

In the above technical solution, by making the surface of the glass material contact the cooling plate, it is easy to realize the heat treatment at different temperatures on both sides of the glass material in the temperature control furnace.

In a possible implementation manner, before performing chemical strengthening treatment on the crystallized glass substrate, the method further includes: performing thermal pre-bending treatment on the glass material.

In the above technical solution, the thermal pre-bending treatment of the glass material can perform and compensate the deformation of the glass material caused by the subsequent asymmetric chemical strengthening, and can avoid the bending of the glass material due to the asymmetric chemical strengthening.

In a third aspect, the present application provides a glass product made of the glass material in the first aspect or any possible implementation manner of the first aspect.

In a fourth aspect, the present application provides an electronic device including a housing having a front surface, a rear surface, and a side surface; an electronic component at least partially located in the housing, the electronic component including at least a controller , A memory and a display, the display is located at or adjacent to the front surface of the housing; and the glass disposed above the display as in the first aspect or in any possible implementation of the first aspect material.

BRIEF DESCRIPTION

Fig. 1 is a schematic diagram of ion exchange.

FIG. 2 is a schematic diagram of the relationship between the surface compressive stress, the depth of the chemically strengthened layer, the depth of the compressive stress layer, and the central tensile stress.

3 is a schematic structural diagram of a glass material according to an embodiment of the present application.

4 is a schematic flowchart of a method for manufacturing a glass material according to an embodiment of the present application.

FIG. 5 is a schematic flowchart of an asymmetric strengthening process according to another embodiment of the present application.

6 is a schematic flowchart of an asymmetric strengthening process according to another embodiment of the present application.

7 is a schematic flowchart of an asymmetric chemical strengthening process according to an embodiment of the present application.

Fig. 8 is a symmetric chemical strengthening stress curve and an asymmetric chemical strengthening stress curve.

9 is a schematic structural diagram of an electronic device according to an embodiment of the present application.

detailed description

The technical solutions in this application will be described below with reference to the drawings.

The glass material of the embodiments of the present application can be applied to electronic devices, for example, cover glass of electronic devices (for example, a front cover of a mobile phone screen, a back cover of a battery, etc.), a housing, and the like.

It should be understood that the glass material of the embodiment of the present application can also be applied to other occasions, as long as there is a place where a glass material with high drop resistance is used in the occasion. For example, for a car, and further, for example, a lampshade, a windshield, or an interior dashboard glass.

In order to facilitate understanding of the solutions of the embodiments of the present application, the concepts and related technologies involved in the present application are described first.

Glass chemical strengthening: Generally, ion exchange method is used for strengthening. As shown in Figure 1, ion exchange is to immerse the glass in a molten salt of alkali metal filled with a larger ionic radius. At the glass transition temperature Tg of the glass, the alkali metal ions of large radius (for example, Na + or K +) in the molten salt ) It exchanges with the small radius alkali metal Li + in the glass surface by ion exchange. The volume difference between the two after ion exchange makes the glass surface appear compressive stress. Generally speaking, the greater the depth of the compressive stress layer, the more helpful it is for the glass's resistance to falling. The types of chemically strengthened glass mainly include soda lime glass, aluminosilicate glass, phosphorous aluminosilicate glass and lithium aluminosilicate glass (for example, the fifth generation gorilla glass GG5 launched by Corning in 2016 in the United States is lithium aluminosilicate glass).

Surface compressive stress (compressive stress) (CS): generally refers to the maximum compressive stress formed on the glass surface by chemically strengthened glass, used to protect the glass surface and suppress the development of surface defects into cracks.

Depth of chemically strengthened layer (DOL): generally refers to the depth to which the enhanced ions used in chemically strengthened glass (such as potassium ions used to strengthen soda glass) diffuse into the glass.

Depth of compressive stress layer (depth) of compression (DOC): generally refers to the thickness of the chemically strengthened glass compressive stress layer, that is, the distance from the surface (where the compressive stress is greatest) to the location where the compressive stress is zero. When the DOL is shallow (for example, DOL <0.1t, t represents the thickness), DOC and DOL are basically the same, but as DOL gradually improves, the difference between DOC and DOL becomes greater and greater, for example, a chemical strengthening to get DOL> At 0.5t, the DOC is generally around 0.21-0.25t. Therefore, in the case of general chemical strengthening, 0.21-0.25t is the maximum value of DOC.

Central tension (CT): Due to the stress balance requirements, the chemically strengthened surface compressive stress and the central tensile stress must be in equilibrium. Due to the existence of central tensile stress, DOC generally has a maximum value, because the thickness of the tensile stress layer of the material must be ensured.

The relationship between the surface compressive stress, the depth of the chemically strengthened layer, the depth of the compressive stress layer, and the central tensile stress can be shown in Figure 2.

Glass-ceramics (glass-ceramics): also known as glass-ceramics, is a material obtained by controlling glass crystallization in the manufacturing process that contains both crystalline and glass phases. Scanning electron microscope (scanning electron microscope), SEM) or transmission electron microscope (TEM) can observe the glass matrix and the microcrystalline particles dispersed in it. Glass-ceramics are generally opaque, but when the crystal particles are smaller than the wavelength of visible light (for example, less than 300 nm), it is possible to obtain transparent glass-ceramics. According to the crystalline phase of the glass-ceramic, the glass-ceramic can achieve a higher fracture toughness than the glass, thereby enhancing the strength of the cover plate product. Transparent glass-ceramics combine the advantages of high transparency of glass and high strength of ceramics, which provides an effective way to improve the drop resistance of ultra-thin glass covers.

Glass-ceramics based on strengthened glass itself can also be chemically strengthened, coupled with the improvement of fracture toughness of microcrystalline particles, chemically strengthened transparent glass-ceramics are very suitable for consumer electronics (mobile phones, wearable electronics, etc.) material. However, the depth of the current chemical strengthening layer of glass-ceramics still has a maximum limit. In general, no matter how the chemical strengthening process is optimized, the maximum chemical strengthening layer depth that can be obtained is between 21% and 25% of the thickness of the glass-ceramic, which still cannot meet the strength requirements of the ultrathin glass cover.

Specifically, take the mobile phone glass cover as an example. For the drop resistance of mobile phones and other electronic products, the choice of glass cover is the most important factor. However, as shown in Table 1, taking mobile phones as an example, the drop height of mainstream product models on the market is very low.

Table 1

产品product	砂纸跌落Sandpaper drop	形态form
Iphone8Iphone8	0.5m时跌落产生裂纹Crack at 0.5m drop	2.5D电池盖2.5D battery cover
三星Note8Samsung Note8	0.7m时跌落产生裂纹Crack at 0.7m	3D电池盖3D battery cover
Mate10Mate10	0.58m时跌落产生裂纹Crack at 0.58m	3D电池盖3D battery cover

The embodiments of the present application provide a glass material that has an ultra-deep chemical strengthening layer depth on at least one side, and thus has better drop resistance.

3 is a schematic structural diagram of a glass material according to an embodiment of the present application. It should be understood that the glass material shown in FIG. 3 is only an example, and the glass material in the embodiments of the present application is not limited thereto.

As shown in FIG. 3, the glass material contains crystals, and the depth of the chemically strengthened layer of at least a part of the side of the glass material is greater than 21% of the thickness, which is the surface of the glass material on one side and the other side of the glass material The distance between the surfaces, the one side is opposite to the other side.

The embodiments of the present application do not specifically limit the types of glass materials, for example, soda lime glass, aluminosilicate glass, phosphorous aluminosilicate glass, lithium aluminosilicate glass, soda aluminosilicate glass, magnesium aluminosilicate glass, and the like.

It should be understood that the glass material may further include other sides, and the embodiments of the present application do not specifically limit the other sides included in the glass material.

It should also be understood that at least part of the area on one side of the glass material and at least part of the area on the other side may have holes, depressions or protrusions, which are not specifically limited in the embodiments of the present application.

The relative of the embodiments of the present application can be understood as relative up and down, left and right, front and back, etc., and the embodiments of the present application are not limited.

In some embodiments, the entire area of the glass material contains crystals.

For example, crystal particles are uniformly or unevenly distributed in all areas of the glass material.

In some embodiments, a portion of the glass material contains crystals.

For example, it may be that the glass material contains crystals that have higher requirements for resistance to falling. Further, for example, when the glass material is applied to a glass cover of an electronic device, part of the area may be the corners, edges, etc. of the glass cover that have higher requirements for resistance to falling.

Optionally, the crystal particles are uniformly or unevenly distributed in a partial area of the glass material.

The uneven distribution of crystal particles in the glass material can also be referred to as uneven crystal content. There are many ways to unevenly distribute the crystal particles in the glass material, and the embodiments of the present application are not specifically limited.

At least part of the area on the glass material side may be the side with a higher crystal content or the side with a lower crystal content.

When the chemical strengthening effect is better in the glass phase, the crystal content on one side of the glass material is lower than the crystal content on the other side.

When the chemical strengthening effect is better in the crystal phase, the crystal content on one side of the glass material is higher than the crystal content on the other side.

In some embodiments, the crystal content of the glass material gradually decreases in a direction from at least a partial area of the starting side to at least a partial area of the ending side, and the starting side is the one side and the other side The one with a higher crystal content in the middle, the end side is the one with a lower crystal content in the one side and the other side, and at least part of the area on the start side is opposite to at least part of the area on the end side.

Alternatively, the crystal content of the glass material gradually decreases to 95% or less of the crystal content of at least part of the area on the starting side.

Alternatively, the crystal content of the glass material gradually decreases to 80% or less of the crystal content of at least part of the area on the starting side.

Alternatively, the crystal content of the glass material gradually decreases to 50% or less of the crystal content of at least part of the area on the starting side.

Optionally, the crystal content of the glass material gradually decreases to zero.

It should be understood that the crystal content of the glass material may be 0 until the end side; it may also be reduced to 0 inside the glass material, and the crystal content is also 0 between the position where the crystal content is reduced to 0 and the end side surface.

When the chemical strengthening effect is better in the glass phase, in some embodiments, the starting side is the other side and the ending side is the side. As an example, as shown in FIG. 3, the crystal content of the glass material gradually decreases along the direction from the entire area on the other side of the glass material to the entire area on the one side of the glass material. As another example, in the direction from the partial region on the other side of the glass material to the partial region on the side of the glass material, the crystal content of the glass material gradually decreases, and the partial region on the other side is opposite to the partial region on one side.

In other embodiments, the crystal content of the glass material gradually decreases along the direction of at least part of the other side of the glass material toward the inside of the glass material, and along the direction of at least part of the glass material toward the inside of the glass material The crystal content of the glass also gradually decreases, and the crystal content on one side of each depth level glass material is lower than the crystal content on the other side. The glass material may contain all crystals inside, or there may be parts without crystals.

When the chemical strengthening effect is better in the crystal phase, in some embodiments, the starting side is the one side and the ending side is the other side. As an example, the crystal content of the glass material gradually decreases in the direction from the entire area on one side of the glass material to the entire area on the other side of the glass material. As another example, the crystal content of the glass material gradually decreases in the direction from the partial region on one side of the glass material to the partial region on the other side of the glass material, and the partial region on the other side is opposite to the partial region on one side.

In other embodiments, the crystal content of the glass material gradually decreases along the direction of at least part of the glass material side toward the inside of the glass material, and along the direction of at least part of the glass material side toward the inside of the glass material. The crystal content also gradually decreases, and the crystal content on one side of each depth level glass material is higher than the crystal content on the other side. The glass material may contain all crystals, or there may be parts that do not contain crystals.

The crystal content of the glass material is different, the volume of the crystal particles is the same, and the distribution density is different; the volume of the crystal particles is different, the distribution density is the same; or the volume and the distribution density of the crystal particles are different, the examples of this application do not make Specific restrictions.

The depth of the chemically strengthened layer on at least part of the glass material side is greater than 21% of the thickness, that is to say, at least part of the area on the glass material side has an ultra-deep chemically strengthened layer depth.

Optionally, the depth of the chemically strengthened layer of at least a part of the side of the glass material is between 21% and 50% of the thickness.

Optionally, the depth of the chemical strengthening layer in at least a part of the side of the glass material is between 21% and 35% of the thickness.

It should be understood that the depth of the chemical strengthening layer in at least part of the area on the other side may be greater than or equal to 21% or 25% of the thickness, or may be much less than 21% of the thickness, which is not limited in the embodiments of the present application.

In some embodiments, when the crystal particles in the glass material are evenly distributed, at least part of the glass material may be asymmetrically chemically strengthened by at least part of the area on one side of the glass material and at least part of the area on the other side. The area has an ultra-deep chemical strengthening layer depth.

Specifically, in some embodiments, a chemical strengthening suppression material may be coated on the surface of at least a part of the other side of the glass material, performing chemical strengthening once, then washing away the chemical strengthening suppressing material, and performing chemical strengthening again, and so on. Until the desired stress curve of the ultra-deep chemical stress layer is obtained. Alternatively, the chemical strengthening suppression material may be a high-temperature ink containing silicon oxide particles.

In other embodiments, at least part of the other side of the glass material may not be contacted with molten salt for chemical strengthening (for example, covering other glass materials, etc.), chemical strengthening is performed once, and then at least part of the glass material is made The surface of the area and the surface of at least a part of the area on the other side are simultaneously in contact with molten salt for chemical strengthening (for example, removing other glass materials covering at least a part of the area on the other side, etc.), and then performing the second chemical strengthening.

In other embodiments, at least part of the area on one side of the glass material may be subjected to chemical strengthening treatment based on the molten salt of the first concentration, and at least part of the area on the other side may be chemical strengthening treatment based on the molten salt of the second concentration. One concentration is higher than the second concentration.

Table 2 lists the correspondence between the difference in the crystal content on both sides of the glass material and the depth DOL of the single-sided chemically strengthened layer of some glass materials in the examples of the present application, where t is the thickness.

Table 2

A	晶体含量差值Difference in crystal content	DOLDOL
玻璃材料1Glass material 1	≥5％≥5%	DOL>0.21tDOL> 0.21t
玻璃材料2Glass material 2	≥20％≥20%	DOL>0.25tDOL> 0.25t
玻璃材料3Glass material 3	≥50％≥50%	0.21t<DOL≤0.5t0.21t <DOL≤0.5t
玻璃材料4Glass material 4	≥100％≥100%	0.21t<DOL≤0.35t0.21t <DOL≤0.35t

It should be understood that the correspondence in Table 2 is only an example, and the embodiments of the present application are not limited thereto. For example, it may be any combination of the above-mentioned difference in crystal content and DOL. The difference in crystal content in Table 2 can also be other values or ranges of values, as long as the values can be within the range of values or values, the glass substrate can be determined to be non-uniformly crystallized. The DOL in Table 2 can also be other values or ranges of values greater than 0.21t.

The embodiments of the present application provide a method for manufacturing a glass material, thereby improving the drop resistance of the glass material.

4 is a schematic flowchart of a method for manufacturing a glass material according to an embodiment of the present application. The method shown in FIG. 4 includes at least part of the following content.

In 410, the glass substrate is subjected to crystallization treatment so that the glass substrate contains crystals.

In 420, the crystallized glass substrate is further subjected to chemical strengthening treatment to obtain a glass material with a chemical strengthening layer depth of at least a partial region on one side greater than 21% of the thickness, the thickness being the crystallized The distance between the surface of one side of the glass substrate and the surface of the other side, the one side being opposite to the other side.

The examples of the present application do not specifically limit the type of glass material, as long as the degree of crystallization can be controlled by controlling the temperature, for example, soda lime glass, aluminosilicate glass, phosphorous aluminosilicate glass, lithium aluminosilicate glass, soda aluminosilicate Glass, magnesium aluminum silicon glass, etc.

Before performing various treatments, the glass material may also be referred to as a glass substrate or a glass substrate.

The crystallization treatment of the glass substrate may be crystallization treatment of all or part of the glass substrate.

Specifically, the crystallization process is performed on a part of the glass substrate, which may be a crystallization process on all regions on one side of the glass substrate, a crystallization process on a part region on one side of the glass substrate, or a glass substrate At least a partial area on one side and at least a partial area on the other side of the glass substrate opposite to the one side are subjected to crystallization treatment or the like.

Alternatively, when crystallization treatment is performed on a partial region of the glass substrate, the partial region may be a part of the glass material that has higher requirements for resistance to falling. For example, when the glass material is applied to a glass cover of an electronic device, the partial area may be a corner or edge of the glass cover that has higher requirements for resistance to falling.

There are various ways to crystallize the glass substrate, for example, heat treatment, laser irradiation, and the like.

Take the heat treatment of a glass substrate to make the glass substrate contain crystals as an example. There are many ways to heat-treat the glass substrate, and the embodiments of the present application are not specifically limited. For example, heat treatment can be carried out in a custom-made single-sided temperature-controlled furnace, and a high-temperature spray gun can be used for heat treatment of glass substrates.

In some embodiments, at least a portion of the other side of the glass substrate is subjected to heat treatment based on a first temperature to crystallize at least a portion of the other side of the glass substrate.

In other words, it is possible to heat-treat one side of the glass substrate so that the glass substrate has crystals on one side.

In other embodiments, at least a portion of the other side of the glass substrate is subjected to heat treatment based on a first temperature to crystallize at least a portion of the other side of the glass substrate A heat treatment based on the second temperature is performed on a part of the regions to crystallize at least a part of the one side.

In other words, heat treatment is performed on both sides of the glass substrate at the same time, so that both sides of the glass substrate contain crystals.

It should be understood that simultaneous heat treatment is understood to mean heating one side of the glass substrate. Due to the thermal conductivity of the glass substrate, the other side of the glass substrate also has a certain temperature, so as to achieve simultaneous heat treatment; it can also be understood as the glass Both sides of the substrate are heated to achieve simultaneous heat treatment.

In some embodiments, the first temperature is the same as the second temperature. In other words, the glass substrate is heated uniformly, so that the crystallization rate on both sides of the glass substrate is the same, and a glass substrate with the same crystal content on both sides can be obtained.

In some embodiments, the first temperature is different from the second temperature. That is to say, the glass substrate is heated unevenly, so that the crystallization rates on both sides of the glass substrate are different, and glass substrates with different crystal contents on both sides can be obtained, that is, glass substrates with uneven crystallization.

It should be understood that the first temperature may be higher than the second temperature or lower than the second temperature.

Take, for example, that the crystal content of at least a part of the region on the other side of the crystallized glass substrate is lower than that of at least a part of the region on one side. When both the first temperature and the second temperature are lower than the temperature most conducive to crystallization of the glass substrate, the first temperature may be lower than the second temperature; when both the first temperature and the second temperature are higher than the most conducive to the glass substrate At the crystallization temperature, the first temperature may be higher than the second temperature; when the second temperature is the temperature most conducive to the crystallization of the glass substrate, the first temperature may be higher than the second temperature or lower than the second temperature temperature.

Specifically, taking the second temperature as the temperature most conducive to the crystallization of the glass substrate as an example, at the same time, heat treatment is performed on at least part of the area on one side of the glass material of the glass substrate and at least part of the area on the other side, but making the glass substrate one The second temperature of at least part of the side is higher than the temperature at which the glass substrate will crystallize but is different from the first temperature, so that the crystallization rate of at least part of the side of the glass substrate will be lower than that of the other side Crystallization rate. After the above-mentioned treatment, a glass substrate (differently crystallized glass substrate) having double-sided crystallization but different degrees of crystallization on both sides can be obtained.

It should be understood that when at least part of the area on one side of the glass material is crystallized, at least part of the area on the side of the glass material contains both the crystal phase and the glass phase, or only the crystal phase; when at least part of the area on the other side of the glass substrate When crystallization occurs, at least a part of the region on the other side may contain both the crystal phase and the glass phase.

Optionally, the first temperature and the second temperature are higher than the temperature at which the glass material crystallizes, and the difference between the first temperature and the second temperature is greater than or equal to 50 degrees.

When the crystal content of at least a part of the other side of the crystallized glass substrate is higher than the crystal content of at least a part of one side, the relationship between the first temperature and the second temperature is opposite to that described above and will not be repeated here.

In some other embodiments, at least part of the area on one side of the glass substrate is processed so that at least part of the area on one side is not crystallized, and at least part of the area on the other side of the glass substrate is subjected to heat treatment based on the first temperature To crystallize at least part of the other side of the glass material.

For example, at least part of the area on the glass substrate side can be cooled so that the temperature of at least part of the glass substrate side is lower than the temperature at which the glass substrate will crystallize, so that at least part of the area on the glass substrate side will not crystallize Change. At the same time, at least part of the area on the other side of the glass substrate is subjected to heat treatment based on the first temperature so that the first temperature is higher than or equal to the temperature at which the glass substrate will crystallize. Crystallization. After the above treatment, a single-sided crystallized glass substrate (uniformly crystallized glass substrate) can be obtained.

It should be understood that no crystallization occurs in at least part of the area on one side of the glass substrate, which means that there is no crystal phase in at least part of the area on the side of the glass substrate, only the glass phase; and at least part of the area on the other side of the glass substrate also contains crystals Phase and glass phase, or only crystalline phase.

In addition to the above technical solutions, there are many ways to cause uneven crystallization of the glass substrate. As an example, the glass substrate may be processed to change the composition of the glass substrate so that uneven crystallization naturally occurs in the same crystallization environment. As another example, in the same crystallization environment, a region of the glass substrate that requires more crystal phases is irradiated with laser light to accelerate the crystallization of the region, thereby obtaining a non-uniformly crystallized glass substrate.

After the above-mentioned crystallization treatment, the crystallized glass substrate is further subjected to chemical strengthening treatment.

The chemical strengthening treatment may be performed on the crystallized glass substrate, which may be a chemical strengthening treatment on all or part of the glass substrate.

When the crystallized glass substrate is a non-uniformly crystallized glass substrate, in some embodiments, at least part of the area on one side of the glass substrate and at least part of the area on the other side may be symmetrically chemically strengthened to obtain At least part of the region on one side has a chemically strengthened layer with a depth greater than 21% of the thickness of the glass material. In other embodiments, at least part of the area on one side of the glass substrate and at least part of the area on the other side may be asymmetrically chemically strengthened to obtain a chemically strengthened layer with a depth of at least part of the area greater than 21 % Glass material.

When the crystallized glass substrate is a uniformly crystallized glass substrate, in some embodiments, at least part of the area on one side of the glass substrate and at least part of the area on the other side may be asymmetrically chemically strengthened to obtain At least part of the region on one side has a chemically strengthened layer with a depth greater than 21% of the thickness of the glass material.

Further, in some embodiments, at least part of the area on one side of the glass substrate and at least part of the area on the other side are chemically strengthened.

In other embodiments, the chemical strengthening may be repeated at least part of the area on one side of the glass substrate and at least part of the area on the other side until the required stress curve of the ultra-deep chemical stress layer is obtained.

After performing a symmetric chemical strengthening treatment on at least part of the area on one side of the glass substrate and at least part of the area on the other side, when it is difficult to obtain the desired stress curve of the ultra-deep chemical stress layer, at least one side of the glass substrate may be further Part of the area and at least part of the other side are asymmetrically chemically strengthened.

There are many methods for asymmetric chemical strengthening, and the embodiments of the present application are not specifically limited.

When the depth of the chemically strengthened layer on at least a part of the glass material is greater than 21% of the thickness, in some embodiments, as shown in FIGS. 5 and 6, by suppressing the chemical strengthening of at least a part of the other side, At least part of the area on one side of the glass substrate and at least part of the area on the other side are asymmetrically chemically strengthened.

Specifically, a chemical strengthening suppression material may be coated on at least part of the other side, perform chemical strengthening once, then wash away the chemical strengthening suppression material, and perform chemical strengthening again, and so on, until the desired ultra-deep chemical stress is obtained The stress curve of the layer.

Alternatively, the chemical strengthening suppression material may be a high-temperature ink containing silicon oxide particles.

In other embodiments, at least part of the area on the other side may not be contacted with molten salt for chemical strengthening (for example, covering other glass materials, etc.), chemical strengthening is performed once, and then at least part of the area on the side of the glass material is made Simultaneously contacting at least part of the area on the other side with molten salt for chemical strengthening (for example, removing other glass materials covering at least part of the area on the other side), and then performing the second chemical strengthening.

In other embodiments, at least part of the area on one side of the glass substrate may be subjected to chemical strengthening treatment based on the molten salt of the first concentration, and at least part of the area on the other side may be chemical strengthening treatment based on the molten salt of the second concentration. One concentration is higher than the second concentration.

In the above technical solution, two surfaces of the glass substrate are in contact with molten salts of different concentrations. Since the chemical strengthening is easier in the molten salt with a larger concentration, this can further expand the difference in the degree of chemical strengthening of at least part of the area on one side of the glass substrate and at least part of the area on the other side, thereby expanding the side of the glass material The difference between the depth of the chemical strengthening layer of at least part of the region and the at least part of the other side makes the depth of the chemical strengthening layer of the first surface greater, further improving the drop resistance of the glass material.

It should be understood that when at least a partial area on one side of the glass substrate and at least a partial area on the other side are repeatedly chemically strengthened, at least a partial area on one side of the glass material and at least a partial area on the other side may be subjected to multiple asymmetries Chemical strengthening.

In the above technical solution, by suppressing the chemical strengthening of at least a part of the other side of the glass material of the glass material, the difference in the degree of chemical strengthening of at least a part of the one side of the glass material and at least a part of the other side of the glass material is expanded to further expand The difference in the depth of the chemically strengthened layer in at least part of the area on one side of the glass material and at least part of the area on the other side makes the depth of the chemically strengthened layer in at least part of the area on one side greater, further improving the drop resistance of the glass material.

When the depth of the chemical strengthening layer of at least a part of the other side of the glass substrate is greater than 21% of the thickness, the chemical strengthening of at least a part of the side of the glass substrate is suppressed. For specific operations, refer to the above technical solutions.

Since asymmetric chemical strengthening will make the compressive stress of the two opposite surfaces of the glass material different, it may cause the glass material to warp, so it is necessary to pre-treat the glass material before performing asymmetric chemical strengthening. Pre-compensation processing will be carried out for the deformation caused by strengthening. For example, the glass material is subjected to a hot bending process.

The above technical solution can avoid bending of the glass material due to asymmetric chemical strengthening.

The method for manufacturing the glass material according to the embodiment of the present application will be described below with reference to specific examples.

Taking glass material as an example of a glass cover, the embodiments of the present application use aluminosilicate glass substrates such as sodium aluminum silicon, lithium aluminum silicon, magnesium aluminum silicon, etc., and add a nucleating agent (also called a nucleating agent, for example, Zirconia, titania, etc.), crystallized during the melting process or during the post-heat treatment (nucleation and growth), so that nano-sized crystal particles (eg, beta quartz, spinel, lithium glow) are distributed in the glass material Stone, lithium-permeable feldspar, cristobalite, etc.) to obtain transparent glass-ceramics. Further, based on the transparent glass-ceramic, chemical strengthening is performed.

7 is a schematic flowchart of a process of asymmetrically strengthened glass-ceramics according to an embodiment of the present application. As shown in FIG. 4, controlling the temperature field during the crystallization process of the glass material can enable the glass material to obtain a non-uniformly crystallized transparent glass-ceramic during the crystallization process. This non-uniformly crystallized transparent glass-ceramic After symmetrical chemical strengthening, an asymmetric strengthening curve can naturally be obtained, and an ultra-deep strengthening layer exceeding 0.21% -0.25% of the thickness of the crystallized glass can be obtained.

The symmetric chemical strengthening stress curve and the asymmetric chemical strengthening stress curve are shown in FIG. 8.

The core flow of the method for manufacturing a glass material according to an embodiment of the present application is as follows: batch preparation → glass melting → glass substrate molding → crystallization → hot bending → polishing → chemical strengthening treatment, which is described as follows.

1) Preparation of batch materials: Alumina, silicon oxide, magnesium oxide, calcium oxide, zinc oxide, alkali metal oxide, nucleating agent and other raw materials are configured according to a certain ratio.

For example, 70% SiO ₂ , 13% Al ₂ O ₃ , 10% Li ₂ O, 5% Na ₂ O, and 2% TiO _2.

2) Glass melting: The above raw materials are put into a melting furnace and melted at a high temperature to obtain a high-temperature glass liquid, and at the same time, bubbles and foreign substances in the glass liquid are removed.

3) Glass substrate molding: the glass raw materials are made into plates by using the mature glass plate forming process such as float method, calendering method, overflow method, and pull-down method.

4) Crystallization: heat treatment is performed during or after the above-mentioned molding process to obtain an unevenly distributed glass-ceramic material.

For example, after the above molding process, heat treatment is carried out in a specially customized single-sided temperature control furnace.

For example, single-sided crystallization at 600 degrees Celsius for 2 hours, long-term crystallization at 750 degrees Celsius for 4 hours, and the other side of the glass material contacts the cooling plate for cooling, so that a microcrystalline glass material with unevenly distributed crystal phases is obtained.

5) 3D hot bending: use a mold to heat bend the glass material to obtain the shape of the 3D cover plate. This model should be pre-compensated for the deformation caused by the subsequent asymmetric chemical strengthening.

6) Chemical strengthening: Place the glass cover plate of the above steps in a salt bath furnace and heat-treat it under the Tg point of the glass. The large radius alkali metal ions in the molten salt and the small radius alkali metal ions in the glass surface undergo ion exchange , Compressive stress is formed on the surface, so as to obtain a glass cover plate with excellent final drop resistance.

7) If a uniformly distributed glass-ceramic material is obtained in step 4), apply a material that inhibits chemical strengthening (for example, a high-temperature ink containing silicon oxide particles) on the single surface of the glass, and then perform the first chemical Strengthen, then wash away the strengthened chemical strengthening inhibiting material and perform secondary strengthening. This is repeated until the required stress curve of the ultra-deep stress layer is obtained.

The glass material obtained by the method for manufacturing a glass material according to the embodiment of the present application has a unilateral chemical strengthening layer with a depth of at least 21% of the thickness. In the best case, it reaches and exceeds 21% of the thickness, but less than 50% of the thickness; The thickness of the surface chemical strengthening layer is much less than 21%.

The present application provides a glass product made of the glass material in any one of the possible implementation manners described above.

The present application provides a glass cover plate for an electronic device. The glass cover plate is made of the glass material in any one of the possible implementation manners described above.

The glass products of the embodiments of the present application can be applied to devices with displays (or display products), for example, electronic devices (including mobile phones, tablet computers, computers, navigation systems, etc.); construction products; transportation products (such as cars, trains, and aircraft) , Ships, etc.), appliance products, or any products that require a certain degree of transparency, scratch resistance, abrasion resistance, or a combination of the above properties.

As shown in FIG. 9, the present application provides an electronic device. The electronic device 900 includes: a housing 901 having a front surface 902, a rear surface 904, and a side surface 903; at least partially located in the housing 901 Internal electronic components (not shown), the electronic components including at least a controller, a memory, and a display 906, the display 906 is located at or adjacent to the front surface of the housing 901; and provided Above the display 906 is the glass material 905 in any of the embodiments described above.

It should be understood that FIG. 9 is only used as an example, and the electronic device in the embodiment of the present application may also be other electronic devices other than a mobile phone, such as a tablet computer, a computer, and a navigation system. It should also be understood that the glass material in the embodiments of the present application may be provided on the front surface of the electronic device case, or may be provided on the rear surface of the electronic device (for example, used as a battery back cover) or a side surface.

The above is only the specific implementation of this application, but the scope of protection of this application is not limited to this, any person skilled in the art can easily think of changes or replacements within the technical scope disclosed in this application. It should be covered by the scope of protection of this application. Therefore, the protection scope of the present application shall be subject to the protection scope of the claims.

Claims

A glass material, characterized in that the glass material contains crystals, and the depth of the chemical strengthening layer in at least a part of the glass material side is greater than 21% of the thickness, and the thickness is the surface of the glass material side and The distance between the surfaces of the other side of the glass material, the one side being opposite to the other side.
The glass material according to claim 1, characterized in that the crystal content of the glass material gradually decreases in a direction from at least part of the starting side to at least part of the ending side, and the starting side is the One of the one side and the other side has a higher crystal content, the end side is the one of the one side and the other side has a lower crystal content, and at least part of the area on the starting side reaches the end At least part of the sides are opposite.
The glass material according to claim 2, wherein the crystal content of the glass material gradually decreases to 95% or less of the crystal content of at least part of the starting side.
The glass material according to claim 2, wherein the crystal content of the glass material gradually decreases to 80% or less of the crystal content of at least part of the starting side.
The glass material according to claim 2, wherein the crystal content of the glass material gradually decreases to 50% or less of the crystal content of at least a part of the starting side.
The glass material according to claim 2, wherein the crystal content of the glass material gradually decreases to zero.
The glass material according to any one of claims 1 to 6, wherein the depth of the chemically strengthened layer of at least a part of the one side is greater than 21% of the thickness and less than or equal to 50% of the thickness .
The glass material according to any one of claims 1 to 6, wherein the depth of the chemically strengthened layer of at least a part of the side is greater than 21% of the thickness and less than or equal to 35% of the thickness .
The glass material according to any one of claims 1 to 8, wherein the depth of the chemical strengthening layer in at least a part of the other side is smaller than the depth of the chemical strengthening layer in at least a part of the one side.
A method for manufacturing glass material, characterized in that it includes:

Crystallizing the glass substrate so that the glass substrate contains crystals;

Further, the crystallized glass substrate is chemically strengthened to obtain a glass material with a chemical strengthening layer depth of at least a part of one side greater than 21% of the thickness, the thickness being one side of the crystallized glass substrate The distance between the surface of the other side and the surface of the other side, the one side being opposite to the other side.
The method according to claim 10, wherein the crystallizing the glass substrate comprises:

A heat treatment based on a first temperature is performed on at least a portion of the other side to crystallize at least a portion of the other side.
The method according to claim 11, wherein the crystallizing the glass substrate further comprises:

A heat treatment based on a second temperature is performed on at least a part of the region on the one side to crystallize at least a part of the region on the one side, and at least a part of the region on the other side is opposite to at least a part of the region on the one side.
The method of claim 12, wherein the first temperature is different from the second temperature.
The method according to any one of claims 10 to 13, wherein the single side is the side;

Before chemically strengthening the crystallized glass substrate, the method further includes:

A chemical strengthening suppression material is coated on at least part of the other side.
The method according to claim 14, wherein the chemical strengthening suppression material is a high-temperature ink containing silicon oxide particles.
The method according to any one of claims 12 to 15, wherein when the first temperature is lower than the second temperature, the first temperature is at least part of the other side of the glass substrate The temperature of the area after cooling by contacting the cooling plate,

Or when the first temperature is higher than the second temperature, the second temperature is the temperature after at least a part of the side of the glass substrate is cooled by contacting the cooling plate.
The method according to any one of claims 10 to 16, wherein before the chemically strengthening the crystallized glass substrate, the method further comprises:

Thermal pre-bending treatment is performed on the glass substrate.
A glass product, characterized in that the glass product is made of the glass material according to any one of claims 1 to 9.
An electronic device, characterized in that it includes:

A casing having a front surface, a rear surface and a side surface;

Electronic components located at least partially within the housing, the electronic components including at least a controller, a memory, and a display, the display being located at or adjacent to the front surface of the housing;

And the glass material according to any one of claims 1 to 9 provided above the display.