阅读说明：本技术 一种用于玻璃原片的晶化的方法 (Method for crystallizing glass original sheet ) 是由 周强 胡恒广 闫冬成 张广涛 王博 李亚迪 姚荣江 于 2021-10-21 设计创作，主要内容包括：本公开涉及一种用于玻璃原片的晶化的方法,该方法包括：将多个玻璃原片层叠放置形成玻璃叠片组,使所述玻璃叠片组进行晶化处理,其中,相邻两层所述玻璃原片之间具有溶剂组合物；所述溶剂组合物包括含氮化合物、金属氧化物和无机盐；以所述溶剂组合物的总重量为基准,所述含氮化合物的含量为40～90重量％,所述金属氧化物的含量为5～60重量％,所述无机盐含量为0.1～20重量％。采用本公开所述的方法,能够降低在晶化过程中的翘曲现象,提高良品率,同时能够提升晶化效率。(The present disclosure relates to a method for crystallization of a glass precursor, the method comprising: stacking a plurality of glass original sheets to form a glass lamination stack, and performing crystallization treatment on the glass lamination stack, wherein a solvent composition is arranged between two adjacent layers of the glass original sheets; the solvent composition comprises a nitrogen-containing compound, a metal oxide and an inorganic salt; based on the total weight of the solvent composition, the content of the nitrogen-containing compound is 40-90 wt%, the content of the metal oxide is 5-60 wt%, and the content of the inorganic salt is 0.1-20 wt%. By adopting the method disclosed by the invention, the warping phenomenon in the crystallization process can be reduced, the yield is improved, and meanwhile, the crystallization efficiency can be improved.)

1. A method for crystallization of a glass precursor, the method comprising:

stacking a plurality of glass original sheets to form a glass lamination stack, and performing crystallization treatment on the glass lamination stack, wherein a solvent composition is arranged between two adjacent layers of the glass original sheets;

the solvent composition comprises a nitrogen-containing compound, a metal oxide and an inorganic salt;

based on the total weight of the solvent composition, the content of the nitrogen-containing compound is 40-90 wt%, the content of the metal oxide is 5-60 wt%, and the content of the inorganic salt is 0.1-20 wt%.

2. The method according to claim 1, wherein the nitrogen-containing compound is selected from one or more of boron nitride, aluminum nitride, magnesium nitride, titanium nitride and tantalum nitride, preferably boron nitride;

the metal oxide is selected from one or more of aluminum oxide, boron oxide, sodium oxide, titanium oxide and zinc oxide, and is preferably aluminum oxide;

the inorganic salt is selected from one or more of sodium chloride, potassium chloride, sodium nitrate, potassium nitrate and sodium sulfate, and is preferably sodium chloride.

3. The method of claim 1, wherein the dimensions of the glass precursor sheet comprise: the length of the glass original sheet is 5-25 cm, the width of the glass original sheet is 5-15 cm, and the thickness of the glass original sheet is 0.07-0.4 cm.

4. The method according to claim 1, wherein the stack of glass laminate sheets comprises from 2 to 30 sheets of the glass precursor sheet, preferably from 5 to 20 sheets of the glass precursor sheet, and more preferably from 10 to 15 sheets of the glass precursor sheet.

5. The method of claim 1, further comprising: spraying the solvent composition on the two side surfaces of each glass raw sheet, and then sequentially laminating the glass raw sheets with the solvent composition sprayed on the surfaces to form the glass lamination stack.

6. The method according to claim 1, wherein the glass original sheet is selected from one or more of a transparent glass original sheet, a translucent glass original sheet, an opaque glass original sheet and a ceramic, preferably a transparent glass original sheet;

the transparent glass original sheet contains SiO₂、Al₂O₃MgO and mixed metal oxides; based on the total weight of the transparent glass original sheet, the SiO₂The content of (b) is 40 to 80 wt%, preferably 35 to 65 wt%; al (Al)₂O₃The content of (b) is 10 to 30 wt%, preferably 20 to 30 wt%; the MgO content is 3 to 15 wt%, preferably 2 to 10 wt%; the content of the mixed metal oxide is 0 to 30 wt%, preferably 2 to 10 wt%; the mixed metal oxide is selected from B₂O₃、Na₂O、K₂O、ZnO、TiO₂And ZrO₂At least two of them.

7. The method of claim 6, wherein the glass precursor is a zinc magnesium spinel system and/or a magnesium aluminum spinel system;

based on the total weight of the glass raw sheet, the content of the magnesium aluminate spinel system is 5-80 wt%;

the magnesium aluminate spinel system is selected from MgAl₂O₄/ZnAl₂O₄、MgTiO₅、TiO₂、MgSiO₃、ZrO₂、Mg₂Al₄Si₅O₁₈Mg-filled beta-quartz and SiO₂One or more of them.

8. The method of claim 1 further comprising stacking silicon carbide plates on top and bottom surfaces, respectively, of the stack of glass laminations, the stack of glass laminations being centered on the silicon nitride plate; carrying out crystallization treatment on the glass lamination stack stacked with the silicon carbide plate; no solvent can be sprayed between the silicon carbide plate and the glass lamination stack;

the density of the silicon carbide plate is 3-3.5 g/cm³。

9. The method according to claim 8, wherein the silicon carbide plate has an area larger than the glass original sheet, and the difference between the lengths of the silicon carbide plate and the glass original sheet is 1 to 10cm, preferably 3 to 5 cm; the difference between the widths of the silicon carbide plate and the glass original sheet is 1-10 cm, preferably 3-5 cm; the thickness of the silicon carbide plate is 0.3-1 cm, and the preferable thickness is 0.7 cm.

10. The method of claim 1, wherein the crystallization conditions comprise: the crystallization temperature is 400-1000 ℃, preferably 530-850 ℃; the crystallization time is 1-24 h, preferably 4-6 h.

Technical Field

The present disclosure relates to the field of glass manufacturing, and in particular, to a method for crystallization of glass flakes.

Background

With the protection and beauty improvement of display devices of smart phones, portable information terminals (PDAs) and tablet terminal mobile devices, there is an increasing demand for various cover glasses, in which a glass original sheet has excellent heat resistance, high infrared transmittance, can provide various shapes, and can be used for various optical purposes, and the market of glass original sheets is mainstream at present due to its superior optical and mechanical properties. Glass flakes are an inorganic material with controlled crystallization obtained by controlled heat treatment, so heat treatment (nucleation, crystallization) is essential in the production of glass flakes. The glass is difficult to produce in batch because the glass is easy to stick together and deform at high temperature, namely, the glass is easy to warp, and most of the companies adopt single-block flat-laying crystallization at present, which causes the increase of cost and the occurrence of warp, and is not beneficial to the mass production of original glass sheets.

Disclosure of Invention

The invention aims to provide a crystallization method capable of laminating crystallization and reducing warping, which is used for solving the problem of difficult batch production caused by easy warping between glass and glass at high temperature.

In order to achieve the above object, the present disclosure provides a method for crystallization of a glass original sheet, the method comprising: stacking a plurality of glass original sheets to form a glass lamination stack, and performing crystallization treatment on the glass lamination stack, wherein a solvent composition is arranged between two adjacent layers of the glass original sheets; the solvent composition comprises a nitrogen-containing compound, a metal oxide and an inorganic salt; based on the total weight of the solvent composition, the content of the nitrogen-containing compound is 40-90 wt%, the content of the metal oxide is 5-60 wt%, and the content of the inorganic salt is 0.1-20 wt%.

Optionally, the nitrogen-containing compound is selected from one or more of boron nitride, aluminum nitride, magnesium nitride, titanium nitride and tantalum nitride, and is preferably boron nitride; the metal oxide is selected from one or more of aluminum oxide, boron oxide, sodium oxide, titanium oxide and zinc oxide, and is preferably aluminum oxide; the inorganic salt is selected from one or more of sodium chloride, potassium chloride, sodium nitrate, potassium nitrate and sodium sulfate, and is preferably sodium chloride.

Optionally, the dimensions of the glass original sheet include: the length of the glass original sheet is 5-25 cm, the width of the glass original sheet is 5-15 cm, and the thickness of the glass original sheet is 0.07-0.4 cm.

Optionally, the glass laminate stack comprises 2 to 30 sheets of the glass raw sheet, preferably 5 to 20 sheets of the glass raw sheet, and further preferably 10 to 15 sheets of the glass raw sheet.

Optionally, the method further comprises: spraying the solvent composition on the surface of each glass raw sheet, and then sequentially laminating the glass raw sheets with the solvent composition sprayed on the surfaces to form the glass lamination stack.

Optionally, the glass original sheet is selected from one or more of a transparent glass original sheet, a semitransparent glass original sheet, an opaque glass original sheet and ceramic, and is preferably a transparent glass original sheet; the transparent glass original sheet contains SiO₂、Al₂O₃MgO and mixed metal oxides; based on the total weight of the transparent glass original sheet, the SiO₂The content of (b) is 40 to 80 wt%, preferably 35 to 65 wt%; al (Al)₂O₃The content of (b) is 10 to 30 wt%, preferably 20 to 30 wt%; the MgO content is 3 to 15 wt%, preferably 2 to 10 wt%; the content of the mixed metal oxide is 0 to 30 wt%, preferably 2 to 10 wt%; the mixed metal oxide is selected from B₂O₃、Na₂O、K₂O、ZnO、TiO₂And ZrO₂In (1)At least two.

Optionally, the glass raw sheet is a zinc magnesium spinel system and/or a magnesium aluminum spinel system; based on the total weight of the glass raw sheet, the content of the magnesium aluminate spinel system is 5-80 wt%; the magnesium aluminate spinel system is selected from MgAl₂O₄/ZnAl₂O₄、MgTiO₅、TiO₂、MgSiO₃、ZrO₂、Mg₂Al₄Si₅O₁₈Mg-filled beta-quartz and SiO₂One or more of them.

Optionally, the method further comprises stacking silicon carbide plates on the upper and lower surfaces of the glass stack, respectively, the glass stack being centered on the silicon nitride plate; carrying out crystallization treatment on the glass lamination stack stacked with the silicon carbide plate; no solvent can be sprayed between the silicon carbide plate and the glass lamination stack; the density of the silicon carbide plate is 3-3.5 g/cm³。

Optionally, the area of the silicon carbide plate is larger than that of the glass original sheet, and the length difference between the silicon carbide plate and the glass original sheet is 1-10 cm, preferably 3-5 cm; the difference between the widths of the silicon carbide plate and the glass original sheet is 1-10 cm, preferably 3-5 cm; the thickness of the silicon carbide plate is 0.3-1 cm, and the preferable thickness is 0.7 cm.

Optionally, the conditions of the crystallization treatment include: the crystallization temperature is 400-1000 ℃, preferably 530-850 ℃; the crystallization time is 1-24 h, preferably 4-6 h.

By adopting the technical scheme, the solvent composition is arranged between the two adjacent layers of the glass original sheets, so that the glass original sheet lamination can be crystallized, the crystallization efficiency is improved, and the production time is reduced; by adopting the method disclosed by the invention, the warping phenomenon in the crystallization process can be reduced, the yield is improved, and the cost is saved.

Additional features and advantages of the disclosure will be set forth in the detailed description which follows.

Drawings

The accompanying drawings, which are included to provide a further understanding of the disclosure and are incorporated in and constitute a part of this specification, illustrate embodiments of the disclosure and together with the description serve to explain the disclosure without limiting the disclosure. In the drawings:

FIG. 1 is a schematic illustration of one embodiment of the present disclosure for crystallization of glass flakes.

Description of the reference numerals

1. Upper layer silicon carbide plate 2 and glass lamination stack

3. And a lower silicon carbide plate.

Detailed Description

The following detailed description of specific embodiments of the present disclosure is provided in connection with the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present disclosure, are given by way of illustration and explanation only, not limitation.

The present disclosure provides a method for crystallization of a glass precursor, the method comprising: stacking a plurality of glass original sheets to form a glass lamination stack, and performing crystallization treatment on the glass lamination stack, wherein a solvent composition is arranged between two adjacent layers of the glass original sheets; the solvent composition comprises a nitrogen-containing compound, a metal oxide and an inorganic salt; the content of the nitrogen-containing compound is 40-90 wt%, preferably 65-85 wt%, based on the total weight of the solvent composition; the content of the metal oxide is 5-60 wt%, preferably 10-20 wt%; the content of the inorganic salt is 0.1 to 20 wt%, preferably 5 to 10 wt%.

By adopting the technical scheme, the solvent composition is arranged between the two adjacent layers of the glass original sheets, so that the glass original sheet lamination can be crystallized, the crystallization efficiency can be improved by 10-15 times, the production time is reduced, and the fund is saved by more than 10 times in the aspects of labor and electricity charge; by adopting the method disclosed by the invention, the warping phenomenon in the crystallization process can be reduced, the yield is improved, and the cost is saved.

In one embodiment, the nitrogen-containing compound is selected from one or more of boron nitride, aluminum nitride, magnesium nitride, titanium nitride and tantalum nitride, preferably boron nitride; the metal oxide is selected from one or more of aluminum oxide, boron oxide, sodium oxide, titanium oxide and zinc oxide, and is preferably aluminum oxide; the inorganic salt is selected from one or more of sodium chloride, potassium chloride, sodium nitrate, potassium nitrate and sodium sulfate, and is preferably sodium chloride.

In this embodiment, the solution composition contains particles of boron nitride and aluminum oxide because the preferred boron nitride and aluminum oxide are insoluble in water. When the solution composition is used, the mixed solvent is required to be uniformly stirred and then is generally sprayed on the surface of glass by using a high-pressure spray head, and the spray head does not have a rigid requirement and can uniformly spray the mixed solvent.

In one embodiment, the composition of the solvent composition comprises: the boron nitride content was 85 wt%, the alumina content was 10 wt%, and the NaCl content was 5 wt%.

In one embodiment, the boron nitride has an average particle size of 36 to 54 μm, preferably 40 to 50 μm; the average particle size of the alumina is 50 to 100 μm, preferably 50 to 60 μm.

In the embodiment, the boron nitride and the aluminum oxide are uniformly distributed on the glass original sheet, so that the adjacent glass original sheets can be isolated while heat is isolated, and then the glass original sheets can be laminated and then crystallized, and the crystallization efficiency is improved.

In one embodiment, a method of making a solvent composition comprises: the content of boron nitride was 75 wt%, the content of alumina was 15 wt%, and the content of NaCl was 10 wt%.

In one embodiment, the dimensions of the glass precursor sheet include: the length of the glass original sheet is 5-25 cm, the width of the glass original sheet is 5-15 cm, and the thickness of the glass original sheet is 0.07-0.4 cm. Preferably, the length of the glass original sheet is 10-20 cm, the width of the glass original sheet is 7-12 cm, and the height of the glass original sheet is 0.07-0.1 cm.

In one embodiment, the stack of glass laminates comprises from 2 to 30 of the glass precursor sheets, preferably from 5 to 20 of the glass precursor sheets, and more preferably from 10 to 15 of the glass precursor sheets.

In one embodiment, the method further comprises: spraying the solvent composition on the surface of each glass raw sheet, and then sequentially laminating the glass raw sheets with the solvent composition sprayed on the surfaces to form the glass lamination stack.

In the above embodiment, the solvent composition is sprayed on the surface of the glass original sheet, for example, the solvent composition is sprayed on the upper surface of the lowermost glass original sheet; spraying a solvent composition on the lower surface of the uppermost glass sheet; the solvent composition is sprayed onto both the upper and lower surfaces of the ratio master in the intermediate position.

In one embodiment, the glass precursor is a zinc magnesium spinel system and/or a magnesium aluminum spinel system; based on the total weight of the glass base sheet, the content of the magnesium aluminate spinel system is 5-80 wt%, and preferably 30-60 wt%.

In one embodiment, the magnesium aluminate spinel system is selected from MgAl₂O₄/ZnAl₂O₄、MgTiO₅、TiO₂、MgSiO₃、ZrO₂、Mg₂Al₄Si₅O₁₈Mg-filled beta-quartz and SiO₂One or more of the above; preferably, the magnesium aluminate spinel system is selected from MgAl₂O₄/ZnAl₂O₄、MgTiO₅、TiO₂、MgSiO₃、ZrO₂、Mg₂Al₄Si₅O₁₈Mg-filled beta-quartz and SiO₂At least two of them.

In one embodiment, the glass original sheet is one or more selected from the group consisting of a transparent glass original sheet, a translucent glass original sheet, an opaque glass original sheet and a ceramic, and is preferably a transparent glass original sheet.

In one embodiment, the transparent glass master comprises SiO₂、Al₂O₃MgO and mixed metal oxides; based on the total weight of the transparent glass original sheet, the SiO₂The content of (b) is 40 to 80 wt%, preferably 35 to 65 wt%; al (Al)₂O₃The content of (b) is 10 to 30 wt%, preferably 20 to 30 wt%; the MgO content is 3 to 15 wt%, preferably 2 to 10 wt%; mixing ofThe content of the metal oxide is 0-30 wt%, preferably 10-25%; the mixed metal oxide is selected from B₂O₃、Na₂O、K₂O、ZnO、TiO₂And ZrO₂At least two of them.

In one embodiment, the preferred mixed metal oxide combination is B₂O₃Mixed metal combinations with ZnO or TiO₂And ZrO₂The mixed-metal combination of (1).

In one embodiment, the method further comprises stacking a silicon carbide plate on each of the top and bottom surfaces of the stack of glass laminations, the stack of glass laminations being centered on the silicon nitride plate; carrying out crystallization treatment on the glass lamination stack stacked with the silicon carbide plate; no solvent can be sprayed between the silicon carbide plate and the glass lamination stack; the density of the silicon carbide plate is 3-3.5 g/cm³Preferably 3.2 to 3.3g/cm³。

In one embodiment, the area of the silicon carbide plate is larger than the area of the glass original sheet, and the length difference between the silicon carbide plate and the glass original sheet is 1-10 cm, preferably 3-5 cm; the difference between the widths of the silicon carbide plate and the glass original sheet is 1-10 cm, preferably 3-5 cm; the thickness of the silicon carbide plate is 0.3-1 cm.

In one embodiment, the conditions of the crystallization process include: the crystallization temperature is 400-1000 ℃, preferably 530-850 ℃, and more preferably 800-830 ℃; the crystallization time is 1-24 h, preferably 4-6 h.

In the embodiment, the silicon carbide plates are respectively stacked on the upper surface and the lower surface of the glass lamination stack, on one hand, the silicon carbide has good thermal conductivity and high temperature resistance, and cannot generate physical and chemical reactions with the surface of the glass in a high-temperature state, and on the other hand, the silicon carbide plates have certain weight; the above-described characteristics of the silicon carbide plate can further reduce the warping phenomenon of the glass original piece during crystallization.

In one embodiment, a method of crystallizing a glass precursor includes:

after the materials are prepared according to the batch proportion, the materials are added into a mixer to be fully stirred uniformly, the mixture is placed in a lifting furnace to be melted, the temperature is kept at 1650 ℃ for 6 hours, the materials are discharged, the temperature of a discharging table is 200 ℃, and the materials are poured and molded. Then processed into 150 x 70 x 0.7mm polished pieces, which were crystallized under different conditions. Specific examples are shown below.

With regard to the apparatus in the above-described embodiment, the specific manner in which each module performs the operation has been described in detail in the embodiment related to the method, and will not be elaborated here.

Examples

The properties of the glass sheets B1 to B6 in the examples are shown in Table 1.

TABLE 1 glass base sheet Properties

	B1	B2	B3	B4	B5	B6
							SiO2	50.05	61	50.5	55.03	46.24	45.74
Al2O3	24.98	20	24.98	24	28.30	28.50
							Na2O	7.59	/	6.41	2.41	2.29	3
ZnO	2.49	2	2.49	2.49	11.24	12.16
							MgO	9.57	8	9.57	9.57	3.2	4
TiO2	0.61	5	2.50	2.5	1	2
							ZrO2	4.72	3	4.0	4	5.22	4
K2O	0.89	/	/	/	/	/
							BaO2	/	/	/	/	2.51	0.6
Colour(s)	Is transparent	Reddish discharge	Is transparent	Yellowing of hair	Is impermeable	Light yellow
							Main crystal phase	MgAl2O4	MgAl2O4	ZnAl2O4	MgAl2O4	MgAl2O4	MgAl2O4
Degree of crystallinity	43.7％	67.3％	63.54％	58.64％	78.96％	56.87％

Example 1

The glass original sheet used was B1, and the solvent composition was: the boron nitride content was 85 wt%, the alumina content was 10 wt%, and the NaCl content was 5 wt%.

Placing a first B1 original sheet on a bottom silicon carbide plate, spraying a solvent on the surface of glass, then overlapping a second glass sheet, spraying a solvent on the second glass sheet, sequentially overlapping 10 glass sheets according to the steps, then covering an upper silicon carbide cover plate, sending into a precision annealing furnace, preserving heat at 700 ℃ for 2h, then heating to 800 ℃ for 4h, cooling along with the furnace until the temperature is reduced to room temperature, taking out crystallized glass, cleaning and waiting for testing.

Example 2

The method for crystallizing a glass original sheet was the same as in example 1, except that the glass original sheet used was B2.

Example 3

The method for crystallizing a glass original sheet was the same as in example 1, except that the glass original sheet used was B3.

Example 4

The method for crystallizing a glass original sheet was the same as in example 1, except that the glass original sheet used was B4.

Example 5

The method for crystallizing a glass original sheet was the same as in example 1, except that the glass original sheet used was B5.

Example 6

The method for crystallizing a glass original sheet was the same as in example 1, except that the glass original sheet used was B6.

Example 7

The process for crystallizing a glass preform is the same as in example 1 except that a silicon carbide plate is not used for the crystallization.

Comparative examples 1 to 6

The method for crystallizing the glass original sheet is the same as the examples 1 to 6, and is different from the method for crystallizing the glass original sheets B1 to B6 by adopting a conventional lamination method, and the conventional crystallization is single-block crystallization.

Test example

The warpage data obtained by measuring with an image measuring instrument by an optical focusing scanning method is shown in table 2.

The term "upper" used in table 2 refers to above, the term "lower" refers to below, "left" refers to left, "right" refers to right, and the term "middle" refers to the middle portion of the corresponding component profile.

TABLE 2 warpage degree of crystallized glass in examples and comparative examples

Classification	Front side	Rear end	Left side of	Right side	In
						Example 1	0.02	0.02	0.03	0.01	0.02
Example 2	0.04	0.02	0.03	0.02	0.03
						Example 3	0.02	0.04	0.06	0.04	0.02
Example 4	0.10	0.07	0.05	0.03	0.02
						Example 5	0.04	0.03	0.04	0.04	0.02
Example 6	0.01	0.05	0.06	0.04	0.03
						Example 7	0.08	0.09	0.11	0.012	0.09
Comparative example 1	0.14	0.25	0.15	0.2	0.15
						Comparative example 2	0.15	0.12	0.08	0.09	0.12
Comparative example 3	0.15	0.13	0.06	0.12	0.3
						Comparative example 4	0.25	0.25	0.25	0.25	0.21
Comparative example 5	0.2	0.21	0.15	0.17	0.23
						Comparative example 6	0.2	0.2	0.21	0.15	0.14

As shown by the data in the table 2, the comparison of the data in the examples 1 to 7 and the data in the comparative examples 1 to 6 shows that the method disclosed by the invention can obviously reduce the warping degree of the glass after crystallization treatment, so that the yield is improved, and the cost is saved; as can be seen from a comparison of the data in examples 1 and 7, the degree of glass warpage after crystallization can be reduced by stacking silicon carbide plates on the upper and lower surfaces of the lamination stack, respectively.

The preferred embodiments of the present disclosure are described in detail with reference to the accompanying drawings, however, the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present disclosure within the technical idea of the present disclosure, and these simple modifications all belong to the protection scope of the present disclosure.

It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. In order to avoid unnecessary repetition, various possible combinations will not be separately described in this disclosure.

In addition, any combination of various embodiments of the present disclosure may be made, and the same should be considered as the disclosure of the present disclosure, as long as it does not depart from the spirit of the present disclosure.