CN111099827A

CN111099827A - Glass plate, manufacturing method thereof and electronic equipment

Info

Publication number: CN111099827A
Application number: CN201811460693.7A
Authority: CN
Inventors: 欧阳辰鑫; 唐中帜; 吕旺春; 司合帅
Original assignee: Huawei Technologies Co Ltd
Current assignee: Huawei Technologies Co Ltd
Priority date: 2018-10-29
Filing date: 2018-12-01
Publication date: 2020-05-05
Anticipated expiration: 2038-12-01
Also published as: CN111099827B; WO2020088221A1

Abstract

The application discloses a glass plate and a manufacturing method thereof, the glass plate comprises a first surface and a second surface which are opposite, the glass plate is a multi-phase composite formed by a microcrystalline phase and a glass phase, and the proportion value of the microcrystalline phase and the glass phase in the glass plate is in a gradient increasing trend from the first surface to the second surface. When the glass plate provided by the application is manufactured into a glass cover plate of an electronic device, the first surface of the glass plate can be manufactured into the outer surface of the glass cover plate, and the second surface of the glass plate can be manufactured into the inner surface of the glass cover plate. In the glass substrate, the ratio of the microcrystalline phase to the glass phase in the glass sheet tends to increase in a gradient manner from the first surface to the second surface of the glass sheet. Therefore, the electronic equipment glass cover plate made of the glass plate has higher intrinsic strength and higher anti-falling performance, and further improves the anti-falling performance of electronic equipment.

Description

Glass plate, manufacturing method thereof and electronic equipment

Technical Field

The application relates to the technical field of electronics and communications, especially, relate to anti shell technical field that falls.

Background

As consumers have increasingly demanded the fall resistance of electronic devices such as mobile phones, glass covers used for the electronic devices are required to have good fall resistance.

In recent years, the glass cover plate of the electronic device is mainly made of chemically strengthened glass, because after the glass is chemically strengthened or toughened, a compressive stress layer with a certain depth is formed on the surface of the glass, so that the strength and the falling resistance of the glass are improved.

However, in view of the trend of ultra-thin glass cover plates, the strength of the ultra-thin glass cover plates cannot be significantly improved by the currently mature chemical strengthening and physical strengthening process methods. Therefore, more and more researches are focused on the microcrystalline glass (or "glass ceramic"), because the microcrystalline glass is a material which contains both a crystal phase and a glass phase and is obtained by controlling the crystallization of the glass in the manufacturing process of the glass, the microcrystalline glass has the advantages of high transparency of the glass, high strength of the ceramic and the like, and an effective way is provided for improving the anti-falling property of the ultrathin glass cover plate.

Disclosure of Invention

In view of the above, the present application provides a glass plate made of glass ceramics and a manufacturing method thereof, so as to improve the falling resistance of the glass plate and further improve the falling resistance of the electronic device.

In addition, based on the glass plate provided above, the application also provides an electronic device comprising the glass plate.

In order to achieve the purpose of the invention, the following technical scheme is adopted in the application:

a first aspect of the present application provides a glass sheet comprising opposing first and second surfaces, the glass sheet being a multi-phase composite formed from a microcrystalline phase and a glass phase, wherein a ratio of the microcrystalline phase to the glass phase within the glass sheet increases in a gradient from the first surface to the second surface.

When the glass plate provided by the first aspect of the present application is made into a glass cover plate of an electronic device, the first surface of the glass plate can be made into an outer surface of the glass cover plate, and the second surface of the glass plate can be made into an inner surface of the glass cover plate. In the glass substrate, the ratio of the microcrystalline phase to the glass phase in the glass sheet tends to increase in a gradient manner from the first surface to the second surface of the glass sheet. Therefore, the glass phase content is larger near the outer surface area of the glass cover plate, so that the chemical strengthening effect of the glass is enhanced, the falling resistance of the glass cover plate is improved, and the microcrystalline phase content is larger near the inner surface area of the glass cover plate, so that the glass cover plate has higher intrinsic strength. Therefore, the electronic equipment glass cover plate made of the glass plate has higher intrinsic strength and higher anti-falling performance, and further improves the anti-falling performance of electronic equipment.

As one possible implementation of the present application, the glass sheet includes two or more layers of crystallized glass.

As one possible implementation manner of the present application, the microcrystalline phase and the glass phase in each of the microcrystalline glass layers are uniformly distributed from the first surface to the second surface.

As one possible implementation manner of the present application, a ratio value of the microcrystalline phase to the glass phase in each of the microcrystalline glass layers increases in a gradient manner from the first surface to the second surface.

As one possible implementation manner of the present application, the rate of increase of the ratio value of the microcrystalline phase to the glass phase in the glass sheet is constant from the first surface to the second surface, or the rate of increase of the ratio value of the microcrystalline phase to the glass phase in the glass sheet gradually increases from the first surface to the second surface; alternatively, the rate of increase in the ratio of the microcrystalline phase to the glass phase in the glass sheet gradually decreases from the first surface to the second surface.

As a possible implementation manner of the present application, the material system of the glass plate is at least one system of soda lime glass, aluminosilicate glass, soda alumina silicate glass, lithium alumina silicate glass or phosphoaluminosilicate glass.

A second aspect of the present application provides a method of manufacturing a glass sheet, the method comprising: preparing an initial glass plate according to a material formula; the initial glass sheet comprises opposing first and second surfaces; and carrying out heat treatment on the first surface and the second surface of the initial glass plate under different temperature conditions, so that the crystallinity of the first surface of the initial glass plate is smaller than that of the second surface, and further obtaining a final glass plate.

The manufacturing method can manufacture the glass plates with different surfaces and different crystallinities by controlling the heat treatment temperature conditions on the different surfaces, so the process for manufacturing the glass plates is simpler and is beneficial to reducing the process cost.

A third aspect of the present application provides an electronic device, including an electronic component and a glass cover plate covering the electronic component, where the glass cover plate is a glass plate provided in any one of the foregoing possible implementation manners of the first aspect, a first surface of the glass plate is an outer surface of the glass cover plate, and a second surface of the glass plate is an inner surface of the glass cover plate; the inner surface is a glass cover plate surface close to the electronic component, and the outer surface is a glass cover plate surface far away from the electronic component.

In the electronic device, the glass cover plate is the glass plate provided in any one of the possible implementations of the first aspect, the first surface of the glass plate is an outer surface of the glass cover plate, the second surface of the glass plate is an inner surface of the glass cover plate, and the ratio of the microcrystalline phase and the glass phase inside the glass plate tends to increase in a gradient manner from the first surface to the second surface of the glass plate. So, be close to glass apron surface region, glass looks content is great, so, be favorable to strengthening glass's chemical strengthening effect to be favorable to improving glass apron's anti falling nature, being close to glass apron internal surface region moreover, the microcrystalline phase content is great relatively, thereby makes glass apron have higher intrinsic strength. Therefore, the glass cover plate of the electronic device, which is made of the glass plate, has higher intrinsic strength and higher anti-falling performance, so that the electronic device has higher anti-falling performance.

As one possible implementation of the present application, the glass cover includes a screen cover of an electronic device.

As one possible implementation of the present application, the glass cover plate includes a back cover plate of an electronic device.

As one possible implementation of the present application, the glass cover plate includes a screen cover plate and a back cover plate of an electronic device.

Compared with the prior art, the method has the following beneficial effects:

based on the above technical solutions, when the glass plate provided by the present application is manufactured as a glass cover plate of an electronic device, the first surface of the glass plate may be manufactured as an outer surface of the glass cover plate, and the second surface of the glass plate may be manufactured as an inner surface of the glass cover plate. In the glass substrate, the ratio of the microcrystalline phase to the glass phase in the glass sheet tends to increase in a gradient manner from the first surface to the second surface of the glass sheet. Therefore, the glass phase content is larger near the outer surface area of the glass cover plate, so that the chemical strengthening effect of the glass is enhanced, the falling resistance of the glass cover plate is improved, and the microcrystalline phase content is larger near the inner surface area of the glass cover plate, so that the glass cover plate has higher intrinsic strength. Therefore, the electronic equipment glass cover plate made of the glass plate has higher intrinsic strength and higher anti-falling performance, and further improves the anti-falling performance of electronic equipment.

Drawings

In order that the detailed description of the present application may be clearly understood, a brief description of the drawings that will be used when describing the detailed description of the present application will be provided.

FIGS. 1A and 1B are schematic views showing an ion exchange process between glass and an alkali metal molten salt having a large ionic radius;

FIG. 2 is a schematic view of the internal structure of a glass plate according to an embodiment of the present disclosure;

FIG. 3 is a schematic diagram of the gradient type with an increased ratio of the microcrystalline phase to the glass phase provided in the examples of the present application;

FIG. 4 is a schematic view of the internal structure of another glass sheet provided in an embodiment of the present application;

FIG. 5 is a schematic view of the internal structure of another glass sheet provided in an embodiment of the present application;

FIG. 6 is a schematic flow chart of one implementation of a method for making a glass sheet provided by an embodiment of the present application;

FIG. 7 is a schematic flow chart of another implementation of a method of manufacturing a glass sheet provided in an embodiment of the present application;

fig. 8 is a schematic structural diagram of an electronic device provided in an embodiment of the present application.

Detailed Description

Before describing the embodiments of the present application, technical terms used in describing the embodiments of the present application will be described.

Chemically strengthened glass: the term "chemically strengthened" or "tempered" means a glass in which a compressive stress layer (compressive stress layer) is formed to a certain depth on the surface of the glass. Due to the existence of the compressive stress layer, the strength and the falling resistance of the glass are improved.

The specific process of the chemical strengthening or toughening is as follows: the glass to be strengthened is immersed in a molten salt of an alkali metal (such as NaNO) which is filled with a larger ionic radius₃Molten salts or KNO₃Molten salt), at a glass transition temperature (Tg), large-radius alkali metal ions such as Na in the molten salt⁺Or K⁺By ion exchange with small radius alkali metal Li in the glass surface⁺And (4) interchanging. The volume difference between the two is caused after ion exchange, so that the glass surface is in a compressive stress state. In general andin other words, the greater the Depth of compressive stress layer (DOL value), the more helpful the glass is in its shatter resistance.

In which, as an example, fig. 1A and 1B show an ion exchange process between glass and an alkali metal molten salt having a large ionic radius.

The microcrystalline glass is a glass in which some nucleating substances are added, and a large number of fine crystals are uniformly precipitated in the glass by means of heat treatment, light irradiation, chemical treatment or the like, thereby forming a dense multiphase complex of a microcrystalline phase and a glass phase.

At present, the preparation method of the microcrystalline glass mainly comprises three types: melting, sintering and sol-gel processes. The melting method is that various oxide raw materials are uniformly mixed, then a certain amount of nucleating agent is added, melting is carried out at 1400-1600 ℃, a desired glass shape is obtained through molding, then heat treatment is carried out, nucleation and growth are carried out at a proper temperature, and finally the microcrystalline glass is prepared.

The sintering method is that various oxide raw materials are uniformly mixed and melted, and then water quenching is carried out to obtain glass slag instead of direct forming, and then the glass slag is ball-milled to obtain glass powder. And granulating and pressing the glass powder into a green body, and sintering and densifying at a proper temperature to obtain the microcrystalline glass product.

The sol-gel method is to hydrolyze the required organic matter such as metal alkoxide or metal inorganic matter such as acetate and nitrate as precursor, using citric acid as catalyst, to form gel, drying the gel to obtain the required glass powder, and then carrying out the processes of molding, sintering and the like to finally obtain the glass-ceramic product.

The flow of the three methods is as follows:

a melting method: batching → melting → shaping → heat treatment → glass ceramics product;

a melting method: burdening → melting → water quenching → ball milling → granulating → molding → sintering → glass ceramics product;

sol-gel method: batching → precursor → sol → gel → drying → shaping → sintering → glass ceramics product.

The microcrystalline glass product obtained by the three preparation methods has two common characteristics:

1) the glass is nucleated and grown to precipitate crystal phases in the sintering or heat treatment process, the crystal phases are all originated from the phase separation process of the glass phase, and the crystal phases are uniformly distributed in the material because the glass phase is fully and uniformly mixed.

2) Due to the presence of the crystalline phase, the proportion of the glassy phase tends to be reduced, impairing the effect of the chemical strengthening. Because the existence of the glass phase is a necessary condition for chemically strengthening the glass, the glass state is a channel for ion exchange, the more spacious the channel is, the more obvious the ion exchange effect is, and the larger the DOL value is, the more resistant the glass is to falling.

The following describes specific embodiments of the present application.

At present, the falling resistance of electronic equipment is poor, and for example, the falling height of the mainstream product models in the market is very low and cannot exceed 1 meter.

And the front cover plate or the rear cover of the screen of the electronic device can be made of a glass plate. As such, to improve the fall resistance of the electronic device, it is necessary to improve the fall resistance of the glass panel used to form the front or rear cover of the screen of the electronic device.

However, the internal structure of the glass cover plate for electronic devices in the related art is uniformly crystallized, and the distribution of the crystal phase and the glass phase in the structure is uniform. Although the intrinsic strength of the inner surface region of the glass cover plate is increased due to the presence of the crystalline phase. At the same time, the chemical strengthening effect is weakened due to the reduction of the glass phase on the outer surface of the glass cover plate, so that both DOL and compressive stress (CS value) are weakened, and the falling resistance is reduced.

It should be noted that, in the embodiment of the present application, the outer surface of the glass cover plate is the surface of the glass cover plate exposed to air, which is the surface far away from the internal structure of the electronic device, and can be directly touched by a user. The inner surface of the glass cover plate is a surface which is in contact with the internal structure of the electronic equipment and can not be touched by a user.

In order to enable the glass cover plate to have higher intrinsic strength and higher falling resistance, the embodiment of the application provides a glass plate, the glass plate is made of microcrystalline glass, and the glass plate is a multi-phase complex formed by a microcrystalline phase and a glass phase. The distribution of the microcrystalline phase and the glass phase in the glass plate is not uniform, and the proportion value of the microcrystalline phase and the glass phase in the glass plate is in a gradient increasing trend from the first surface to the second surface of the glass plate. Thus, when the glass plate is manufactured into a glass cover plate of an electronic device, the first surface of the glass plate can be manufactured into the outer surface of the glass cover plate, and the second surface of the glass plate can be manufactured into the inner surface of the glass cover plate.

Because the glass phase is a necessary condition for chemically strengthening the glass in the glass ceramics, the glass phase is an ion exchange channel in the chemical strengthening treatment process, the more the glass phase, the more the ion exchange channel is wide, the more obvious the ion exchange effect is, the deeper the compressive stress layer is, and the better the falling resistance of the glass is. The presence of the microcrystalline phase increases the intrinsic strength of the glass. Therefore, when the glass plate provided by the application is made into a glass cover plate of an electronic device, the first surface of the glass plate can be made into the outer surface of the glass cover plate, and the second surface of the glass plate can be made into the inner surface of the glass cover plate. In the glass substrate, the ratio of the microcrystalline phase to the glass phase in the glass sheet tends to increase in a gradient manner from the first surface to the second surface of the glass sheet. Therefore, the glass phase content is larger near the outer surface area of the glass cover plate, so that the chemical strengthening effect of the glass is enhanced, the falling resistance of the glass cover plate is improved, and the microcrystalline phase content is larger near the inner surface area of the glass cover plate, so that the glass cover plate has higher intrinsic strength. Therefore, the electronic equipment glass cover plate made of the glass plate has higher intrinsic strength and higher anti-falling performance, and further improves the anti-falling performance of electronic equipment.

As an implementation manner of the present application, a schematic diagram of an internal structure of a glass plate provided by the present application can be shown in fig. 2. In fig. 2, the black dots indicate crystallites in the glass sheet. As can be seen from fig. 2, the microcrystalline phase inside the glass sheet provided by the present application is non-uniformly distributed in the glass phase, and the proportion of the microcrystalline phase increases in a gradient manner from the first surface S1 to the second surface S2 of the glass sheet.

In the present embodiment, the gradient of the increasing trend of the ratio value of the microcrystalline phase to the glass phase may be a constant value, a continuously increasing variation value, or a continuously decreasing variation value. More specifically, the gradient type may be as shown in fig. 3.

Wherein curve 1 shows a continuous increase in gradient indicating that the rate of increase of the value of the ratio of the microcrystalline phase to the glass phase gradually increases from the first surface to the second surface, and curve 2 shows a constant gradient indicating that the rate of increase of the value of the ratio of the microcrystalline phase to the glass phase does not change from the first surface to the second surface. Curve 3 shows a continuous decrease in the gradient, which means that the rate of increase of the value of the ratio of microcrystalline phase to glassy phase gradually decreases from the first surface to the second surface.

It should be noted that in the present embodiment, the glass plate may be composed of a microcrystalline glass layer, as shown in fig. 2. The crystallinity in the microcrystalline glass layer is not uniformly distributed, and the crystallinity tends to increase in a gradient manner from the first surface to the second surface, so that the ratio of the microcrystalline phase to the glass phase in the glass sheet tends to increase in a gradient manner from the first surface to the second surface.

As another implementation of the present application, a glass sheet may include two layers of crystallized glass. As an example, the glass sheet shown in fig. 4 includes two microcrystalline glass layers including the first microcrystalline glass layer 41 and the second microcrystalline glass layer 42 which are stacked in this order from the first surface S1 toward the second surface S2. The crystallinity of the first glass ceramic layer 41 is smaller than that of the second glass ceramic layer 42, so that the ratio of the microcrystalline phase to the glass phase in the first glass ceramic layer 41 is smaller than that in the second glass ceramic layer 42, so that the ratio of the microcrystalline phase to the glass phase in the glass sheet tends to increase in a gradient manner from the first surface S1 to the second surface S2 in the glass sheet shown in fig. 4.

As an alternative example of the present application, the crystallinity may be the same at each position inside the first microcrystalline glass layer 41, so that the microcrystalline phase and the glass phase inside thereof are in a uniform distribution state. Similarly, the crystallinity in the second microcrystalline glass layer 42 is uniform, and thus the microcrystalline phase and the glass phase in the inside are uniformly distributed.

As another alternative example of the present application, the crystallinity inside the first crystallized glass layer 41 and the second crystallized glass layer 42 gradually increases from the first surface to the second surface of the glass plate, so that the ratio value of the crystallized phase to the glass phase in each crystallized glass layer has a gradient increasing tendency.

As yet another implementation of the present application, a glass sheet may include two or more layers of crystallized glass. As an example, fig. 5 shows a glass plate comprising 5 glass-ceramic layers. Specifically, the glass sheet includes, in order from the first surface S1 to the second surface S2 thereof, a first crystallized glass layer 51 to a fifth crystallized glass layer 55 which are laminated. The crystallinity of the first microcrystalline glass layer 51 to the fifth microcrystalline glass layer 55 increases in sequence, so that the ratio of the microcrystalline phase to the glass phase increases in a gradient manner from the first microcrystalline glass layer 51 to the fifth microcrystalline glass layer 55.

Similar to the glass plate shown in fig. 4, the crystallinity of each microcrystalline glass layer may be the same at each position, so that the microcrystalline phase and the glass phase are uniformly distributed.

As another alternative example of the present application, the crystallinity inside each of the microcrystalline glass layers gradually increases from the first surface S1 to the second surface S2 of the glass sheet, so that the ratio of the microcrystalline phase to the glass phase in each of the microcrystalline glass layers tends to increase in a gradient manner.

In the above-described specific implementation manner of the glass plate provided in the embodiments of the present application, the material system of the glass plate may be at least one system of soda lime glass, aluminosilicate glass, soda alumina silicate glass, lithium alumina silicate glass, or phosphoaluminosilicate glass.

Based on the specific implementation of the glass plate provided by the above embodiment, the application also provides a specific implementation of the manufacturing method of the glass plate.

Referring to fig. 6, a method for manufacturing a glass plate according to an embodiment of the present disclosure includes the following steps:

s601: and preparing various glass green tapes with different crystallization capacities according to different material formulas.

In the present embodiment, a plurality of glass green tapes with different crystallization abilities can be manufactured by using the same or different manufacturing process conditions according to a plurality of material formulas. Wherein the composition of each glass green tape may be different.

By way of example, a method of forming a green glass ribbon according to a material formulation specifically includes the steps of:

s6011: preparing a batch: raw materials for manufacturing the glass plate are configured according to the material formula.

The step may specifically be: the raw materials of alumina, silicon oxide, magnesium oxide, calcium oxide, zinc oxide, alkali metal oxide, nucleating agent and the like are prepared according to a certain proportion.

S6012: melting glass: and putting the prepared raw materials into a smelting furnace, and melting the raw materials to obtain molten glass.

The step may specifically be: the prepared raw materials are put into a smelting furnace and melted at high temperature to obtain high-temperature molten glass, and bubbles, foreign matters and the like in the molten glass are removed.

S6013: water quenching: and pouring the glass liquid into normal-temperature water, and performing water quenching to obtain the glass slag.

The step may specifically be: and (3) after the obtained high-temperature glass liquid is subjected to heat preservation, quickly pouring the high-temperature glass liquid into water, and performing water quenching to obtain glass slag.

S6014: ball milling: and carrying out ball milling and refining on the glass slag to obtain glass powder.

The step may specifically be: and (3) taking a medium related to the glass component as a ball milling medium (such as alumina corundum balls), and carrying out ball milling and refining on the glass slag obtained by water quenching to obtain glass powder.

S6015: sieving and grading: and sieving and grading the glass powder to obtain the glass powder meeting the required particle size distribution.

S6016: pulping: and (3) taking the glass powder meeting the required particle size distribution as a base material, adding an auxiliary agent, and mixing to obtain the glass slurry.

The step may specifically be: and taking the glass powder meeting the required particle size distribution as a base material, adding a certain proportion of solvent, plasticizer, binder and the like, and fully mixing in a batching machine to obtain the glass slurry.

S6017: glass green tape: and carrying out tape casting on the glass slurry to obtain the glass green tape.

The step may specifically be: the glass slurry is used as a raw material, casting molding is carried out on a casting machine (a scraper type casting machine or a coating type casting machine and the like) to prepare a continuous glass green tape, and a sheet of the glass green tape is cut according to the required size.

S602: laminating: according to the gradient requirement of the proportion change of the microcrystalline phase and the glass phase, a plurality of glass green tapes with different crystallization capacities are sequentially overlapped and pressed together according to the size sequence of the crystallinity.

S603: and (6) discharging the glue.

The step may specifically be: the laminated product is put into a glue discharging furnace and is kept warm at a certain temperature, so that high molecular substances such as a solvent, a plasticizer, a binder and the like mixed in the pulping process are decomposed and discharged.

S604: and (5) sintering.

The step may specifically be: and sintering the product in a sintering furnace according to a heating curve and a heat preservation curve of design requirements. Because the glass green tapes with different material formulas have different crystallization capacities, various glass green tapes in the product can show crystallization and nucleation in different degrees, namely, the glass green tapes with different sizes in the same sintering environment.

S605: and (5) post-treatment.

The step may specifically be: and (3) carrying out technological treatment such as grinding, numerical control machine tool machining, polishing and the like on the product obtained in the step to obtain the initial glass plate with the appearance size meeting the design requirement of the terminal product.

S606: and (5) performing chemical strengthening treatment.

The step may specifically be: and placing the initial glass plate in a salt bath furnace, carrying out heat treatment below the glass transition temperature, carrying out ion exchange on large-radius alkali metal ions in molten salt and small-radius alkali metal ions in the surface of the initial glass plate, and forming a pressure stress layer with a specific depth in the surface region of the initial glass plate so as to obtain the final glass plate. The resulting final glass sheet is excellent in shatter resistance.

The method for producing a glass sheet provided by the present application will be described in further detail below with reference to specific examples. The following examples are merely illustrative of the present application and should not be construed as limiting the present application.

Example 1

For example, the material composition of the method for manufacturing a glass plate provided in example 1 is described by taking a lithium aluminum silicon system as an example, and the material formulations are described by taking 3 material formulations as an example. Three material formulas are respectively set as follows: material A, material B and material C.

The manufacturing method of the glass plate shown in this example includes the steps of:

the method comprises the following steps: batch preparation

Calculated according to the mass ratio, the material A contains 55 percent of SiO₂、25％Al₂O₃、12％Na₂O、7％Li₂O、1％TiO₂In which TiO is₂As the primary nucleating agent.

Material B contains 55% SiO₂、25％Al₂O₃、11％Na₂O、7％Li₂O、2％TiO₂。

Material C contains 55% SiO₂、25％Al₂O₃、10％Na₂O、7％Li₂O、3％TiO₂。

Step two: melting of glass

The raw materials of the 3 components are respectively put into a high-temperature melting furnace to be melted at 1500-1600 ℃ for 4-6 h to obtain the high-temperature glass liquid.

Step three: water quenching

And (3) after heat preservation is carried out on the high-temperature glass liquid with the above 3 material formulas, respectively and rapidly pouring the high-temperature glass liquid into water for water quenching, and respectively obtaining 3 types of glass slag.

Step four: ball mill

3 types of glass slag obtained by water quenching are respectively placed in a corundum ball milling tank, the ball milling medium is absolute ethyl alcohol, the ball-material ratio is 5-10, the rotating speed is 400-600 r/m, and the glass powder with the particle size distribution of 1-8 mu m is obtained after ball milling for 4-8 h.

Step five: sieving and grading

And respectively sieving and grading the 3 kinds of glass powder to obtain glass powder A, glass powder B and glass powder C with the particle size distribution of 0.5-4 mu m.

Step six: pulping

3 kinds of glass powder A, B and C are taken as basic materials respectively, a certain proportion of solvent, plasticizer, binder and the like are added, and the materials are fully mixed for 2 to 6 hours in a proportioning machine to respectively prepare 3 kinds of glass slurry suitable for a coating type casting machine.

It should be noted that the selection of the types and contents of the solvent, plasticizer and binder is closely related to the functional parameters of the casting machine in the next step. For example, 50-70% of isobutanol as a solvent, 10-20% of polyvinyl butyral (PVB) as a binder, and 10-20% of polyethylene glycol as a plasticizer are used.

Step seven: glass green tape

The 3 kinds of glass slurry are used as raw materials, and cast molding is carried out on a coating type casting machine and the like to prepare a continuous glass green tape with the thickness of 10-70 mu m. Then cut into a green glass ribbon A, a green glass ribbon B and a green glass ribbon C with the sizes of 180mm and 100 mm.

Step eight: laminating press

And sequentially stacking and pressing 5-100 glass green tapes A, 5-100 glass green tapes B and 5-100 glass green tapes C from top to bottom to respectively obtain the stacked glass plates.

Step nine: glue discharging

And (3) discharging glue for 2h-5h at 300 ℃ -500 ℃ of the laminated glass plate obtained by laminating, and chemically decomposing and discharging auxiliary agents such as isobutanol, polyvinyl acetal butyraldehyde and polyethylene glycol in the glass raw belt.

Step ten: sintering

And immediately sintering the glass plate after the glue is removed at the temperature of 700-900 ℃ for 0.5-1 h. Because of different components in the glass green tape A, the glass green tape B and the glass green tape C, the content of the nucleating agent is different, and crystallization is carried out to different degrees, thereby obtaining glass plates with different crystallinities.

Step eleven: post-treatment

And (3) carrying out grinding, numerical control machine tool machining, polishing and other processes on the glass plates with different crystallinities obtained in the steps to obtain the initial glass plate with the appearance size meeting the design requirement of the terminal product.

Step twelve: chemical strengthening

Placing the 3 kinds of initial glass cover plates in KNO with the mass fraction of 30-50%₃50% -90% of NaNO₃In the molten salt and molten salt, ion exchange is carried out under the strengthening conditions of 400-600 ℃ and 2-6h, so that the compressive stress is formed on the surface of the glass, and the strength of the product is improved.

The above is a specific embodiment of the method for manufacturing a glass plate provided in example 1 of the present application. In the specific implementation mode, 3 kinds of glass components with different crystallization capacities are designed, and then are subjected to pulping and tape casting to obtain 3 kinds of glass green tapes. According to the requirements of gradient design, 3 kinds of glass green tapes can be regularly laminated. In this example, the glass component near one surface (outer (upper) surface) of the glass sheet has poor devitrification ability, and the glass component near the other surface (inner (lower) surface) of the glass sheet has excellent devitrification ability. During sintering, due to the difference of crystallization capacities, the glass plate presents non-uniform crystallized glass with gradient distribution inside. Moreover, the glass phase of the outer (upper) surface of the glass plate accounts for more, which is beneficial to the chemical strengthening treatment in the later period, and the deeper compressive stress layer is formed by more effective ion exchange, thereby being beneficial to improving the anti-falling performance of the glass plate,

The glass plate manufactured by the specific implementation mode has a crystallization structure with certain regularity and gradient distribution in the inner part, and is not the microcrystalline glass with uniform crystallization obtained by the prior art.

Example 2

For example, the material composition of the method for manufacturing a glass sheet provided in example 2 is described with respect to a soda lime system, and the material formulations are described with respect to 5 material formulations. Three material formulas are respectively set as follows: material A, material B, material C, material D and material E.

the method comprises the following steps: batch preparation

The material A contains 70 percent of SiO calculated according to the mass ratio₂、3％Al₂O₃、12％Na₂O、14％CaO₂、1％(TiO₂+ZrO₂) In which TiO is₂+ZrO₂As a composite nucleating agent, facilitates the removal of TiO₂The problem of coloring.

Material B contains 70% SiO₂、3％Al₂O₃、11％Na₂O、14％CaO₂、2％(TiO₂+ZrO₂)。

Material C contains 70% SiO₂、3％Al₂O₃、10％Na₂O、14％CaO₂、3％(TiO₂+ZrO₂)。

Material D contains 70% SiO₂、3％Al₂O₃、9％Na₂O、14％CaO₂、4％(TiO₂+ZrO₂)。

Material E contains 70% SiO₂、3％Al₂O₃、8％Na₂O、14％CaO₂、5％(TiO₂+ZrO₂)。

Step two: melting of glass

The raw materials of the 5 components are respectively put into a high-temperature melting furnace to be melted at the temperature of 1500-1600 ℃ for 4-6 h, and the high-temperature glass liquid is obtained.

Step three: water quenching

And (3) after heat preservation is carried out on the high-temperature glass liquid with the above 5 material formulas, respectively and rapidly pouring the high-temperature glass liquid into water, and carrying out water quenching to respectively obtain 5 types of glass slag.

Step four: ball mill

The specific process conditions of this step are the same as the ball milling process conditions in example 1, and for the sake of brevity, detailed description is omitted here, and specific reference is made to example 1.

Step five: sieving and grading

And sieving and grading the glass powder to obtain glass powder A, glass powder B, glass powder C, glass powder D and glass powder E with the particle size distribution of 0.5-4 mu m.

Step six: pulping

The preparation method comprises the steps of taking 5 types of glass powder as a base material, matching and adopting 50-70% of isobutanol by mass as a solvent, 10-20% of polyvinyl acetal butyraldehyde (PVB) as a binder and 10-20% of polyethylene glycol as a plasticizer, and fully mixing for 2-6 hours in a proportioning machine to respectively prepare 5 types of glass slurry suitable for a coating type casting machine.

Step seven: glass green tape

5 kinds of glass slurry are used as raw materials, and cast molding is carried out on a coating type casting machine and the like to prepare a continuous glass green tape with the thickness of 10-70 mu m. Then cut into a green glass ribbon A, a green glass ribbon B, a green glass ribbon C, a green glass ribbon D and a green glass ribbon E with the size of 180mm gamma 100 mm.

Step eight: laminating press

And sequentially stacking and pressing 3-50 glass green tapes A, 3-50 glass green tapes B, 3-50 glass green tapes C, 3-50 glass green tapes D and 3-50 glass green tapes E from top to bottom to respectively obtain the stacked glass plates.

Step nine: glue discharging

The specific process conditions of this step are the same as those of the glue discharging process in embodiment 1, and for the sake of brevity, detailed description is omitted here, and please refer to embodiment 1 specifically.

Step ten: sintering

The specific process conditions of this step are the same as the sintering process conditions in example 1, and for the sake of brevity, detailed description is omitted here, and specific reference is made to example 1.

Step eleven: post-treatment

The specific process conditions of this step are the same as those of the post-treatment process conditions in embodiment 1, and for the sake of brevity, detailed description is omitted here, and specific reference is made to embodiment 1.

Step twelve: chemical strengthening

The specific process conditions of this step are the same as those of the chemical strengthening process in example 1, and for the sake of brevity, detailed description is omitted here, and specific reference is made to example 1.

The above is a specific embodiment of the method for manufacturing a glass plate provided in example 2 of the present application. In the specific implementation mode, 5 kinds of glass components with different crystallization capacities are designed, and then are subjected to pulping and tape casting to obtain 5 kinds of glass green tapes. The higher crystal phase ratio near one surface (outer (upper) surface) of the glass plate is beneficial to improving the intrinsic strength of the glass plate, the higher crystal phase ratio near the other surface (inner (lower) surface) of the glass plate is beneficial to obtaining higher CS value and DOL value, and the asymmetric structure is more suitable for the ultra-thinning trend of the glass cover plate.

The glass plate manufactured by the specific implementation mode has a remarkable gradient crystallization structure inside the glass plate, and the difference of the internal crystalline phase proportion of the microcrystalline glass cannot be realized by the prior art.

The above is one implementation of the glass plate manufacturing method provided in the embodiments of the present application. In this implementation, glass sheets of differing crystallinity are obtained internally by laminating glass green tapes made from multiple material formulations.

As an extension of the examples of the present application, obtaining a glass sheet with internal crystallinity can also be achieved by different heat treatment conditions, see in particular the following examples.

Referring to fig. 7, another implementation manner of the glass plate manufacturing method provided by the embodiment of the present application includes the following steps:

s701: preparing an initial glass plate according to a material formula; the initial glass sheet includes opposing first and second surfaces.

It should be noted that this step may produce the starting glass sheet in the same manner as the green glass ribbon in the above-described implementation.

For brevity, detailed information may refer to a specific implementation of S601 in the above-described implementations, which will not be described in detail herein.

S702: and carrying out heat treatment on the first surface and the second surface of the initial glass plate under different temperature conditions to ensure that the crystallinity of the first surface of the initial glass plate is less than that of the second surface, thereby obtaining the final glass plate.

Since the crystallinity of a material is related to the temperature during the crystallization process, the crystallinity of the material can be controlled by controlling the temperature during the crystallization process.

Therefore, the present example makes the crystallinity of both surfaces of the initial glass sheet different by performing the heat treatment of both surfaces of the initial glass sheet under different temperature conditions. Specifically, the crystallinity of the first surface of the initial glass sheet is made smaller than the crystallinity of the second surface, thereby obtaining a final glass sheet. The finally obtained glass plate has excellent anti-falling performance on the premise of higher intrinsic strength.

Based on the glass plate that above-mentioned embodiment provided, this application still provides an electronic equipment.

Referring to fig. 8, an electronic device provided in an embodiment of the present application includes: an electronic component 81 and a glass cover plate 82 covering the electronic component 81, wherein the glass cover plate 82 may be a glass plate as described in any of the above implementation manners, and a first surface of the glass plate is an outer surface of the glass cover plate 82, and a second surface of the glass plate is an inner surface of the glass cover plate 82;

the inner surface is a glass cover surface close to the electronic component 81, and the outer surface is a glass cover surface far from the electronic component 82.

Because the distribution of the microcrystalline phase and the glass phase in the glass plate is not uniform, and the ratio value of the microcrystalline phase and the glass phase in the glass plate tends to increase in a gradient manner from the first surface to the second surface of the glass plate. Thus, the glass cover plate 82 made from the glass plate has a higher content of microcrystalline phases in the region near the inner surface of the glass cover plate, resulting in a glass cover plate with higher intrinsic strength. And the area close to the outer surface of the glass cover plate has higher glass phase content, so that the chemical strengthening effect of the glass is favorably enhanced, and the falling resistance of the glass cover plate is favorably improved. Therefore, in the glass cover plate of the electronic device provided by the embodiment of the application, the glass cover plate has higher intrinsic strength and higher anti-falling performance, and the anti-falling performance of the electronic device is further improved.

It should be noted that the electronic device generally includes a front side and a back side, wherein the front side is generally provided with a screen, and the back side is provided with a battery, wherein both the screen and the battery need to be protected by a cover plate, and therefore, as a specific example of the present application, the glass cover 82 may include a screen cover 821 of the electronic device and may also include a back cover 822 of the electronic device. In addition, the glass cover 82 may include both a screen cover 821 and a back cover 822 of the electronic device.

The above provides a specific implementation manner for the embodiment of the present application.

Claims

1. A glass sheet comprising a first surface and a second surface opposite to each other, wherein the glass sheet is a multi-phase composite comprising a microcrystalline phase and a glass phase, and wherein a ratio of the microcrystalline phase to the glass phase in the glass sheet increases in a gradient manner from the first surface to the second surface.

2. The glass sheet according to claim 1, wherein the glass sheet comprises two or more layers of crystallized glass.

3. The glass sheet according to claim 2, wherein the microcrystalline phase and the glass phase in each of the microcrystalline glass layers are uniformly distributed from the first surface to the second surface.

4. The glass sheet according to claim 2, wherein the ratio of the microcrystalline phase to the glass phase in each of the microcrystalline glass layers increases in a gradient from the first surface to the second surface.

5. Glass sheet according to any of claims 1 to 4, characterized in that the rate of increase of the value of the proportion of microcrystalline phase to glass phase inside the glass sheet is constant from the first surface to the second surface,

or the increasing rate of the ratio value of the microcrystalline phase to the glass phase in the glass plate gradually increases from the first surface to the second surface;

alternatively, the first and second electrodes may be,

the rate of increase of the ratio value of the microcrystalline phase to the glass phase in the glass sheet gradually decreases from the first surface to the second surface.

6. Glass sheet according to any one of claims 1 to 5, characterized in that the material system of the glass sheet is at least one of a soda lime glass, an alumino silica glass, a soda alumina silica glass, a lithium alumino silica glass or a phosphoalumino silica glass.

7. A method of manufacturing a glass sheet, the method comprising:

preparing an initial glass plate according to a material formula; the initial glass sheet comprises opposing first and second surfaces;

and carrying out heat treatment on the first surface and the second surface of the initial glass plate under different temperature conditions, so that the crystallinity of the first surface of the initial glass plate is smaller than that of the second surface, and further obtaining a final glass plate.

8. An electronic device comprising an electronic component and a glass cover plate covering the electronic component, wherein the glass cover plate is the glass plate of any one of claims 1-6, the first surface of the glass plate is an outer surface of the glass cover plate, and the second surface of the glass plate is an inner surface of the glass cover plate;

the inner surface is a glass cover plate surface close to the electronic component, and the outer surface is a glass cover plate surface far away from the electronic component.

9. The electronic device of claim 8, wherein the glass cover comprises a screen cover of the electronic device.

10. The electronic device of claim 8, wherein the glass cover plate comprises a back cover plate of the electronic device.

11. The electronic device of claim 8, wherein the glass cover plate comprises a screen cover plate and a back cover plate of the electronic device.