CN110981226A

CN110981226A - Vacuum glass with one-step completion of support and sealing material and preparation method thereof

Info

Publication number: CN110981226A
Application number: CN201911416617.0A
Authority: CN
Inventors: 赵青南
Original assignee: Wuhan University of Technology WUT
Current assignee: Wuhan University of Technology WUT
Priority date: 2019-12-31
Filing date: 2019-12-31
Publication date: 2020-04-10

Abstract

本发明公开了一种支撑物与封接料一次完成的真空玻璃及其制备方法。该方法以低温玻璃粉和低膨胀微晶玻璃粉为原料，通过3D打印、丝网印刷或喷涂的方式在清洁的玻璃表面同时制备出支撑物阵列和封接料，烘干后盖上另外一块玻璃完成组装，最后转移至真空加热炉内进行热处理得到平板或弧面真空玻璃。本发明方法中支撑物与封接料同时布置在玻璃表面上，且在真空高温环境下同时一次成型，极大的降低了支撑物与玻璃接触部位的应力及导热系数，具有工艺简单、效率高、产品质量好等诸多优点。The invention discloses a vacuum glass in which a support and a sealing material are completed at one time and a preparation method thereof. The method uses low-temperature glass powder and low-expansion glass-ceramic powder as raw materials, and simultaneously prepares a support array and a sealing material on a clean glass surface by means of 3D printing, screen printing or spraying, and covers another piece after drying. The glass is assembled and finally transferred to a vacuum heating furnace for heat treatment to obtain flat or curved vacuum glass. In the method of the invention, the support and the sealing material are arranged on the glass surface at the same time, and they are simultaneously formed in a vacuum high temperature environment, which greatly reduces the stress and thermal conductivity of the contact part between the support and the glass, and has the advantages of simple process and high efficiency. , good product quality and many other advantages.

Description

Vacuum glass with one-step completion of support and sealing material and preparation method thereof

Technical Field

The invention relates to the technical field of inorganic non-metallic materials, in particular to vacuum glass with a support and a sealing material completed at one time and a preparation method thereof.

Background

The vacuum glass is generally composed of two sheets of glass, which are separated by a gap of (0.1-0.5) mm with a supporter, and the edge portions of the glass are sealed with a low melting point glass or a metal seal material, thereby forming a vacuum (air pressure lower than 0.1Pa) between the two sheets of glass. The vacuum glass belongs to one of energy-saving glass, the energy-saving principle of the vacuum glass is the common principle of a glass thermos bottle, and the aim of saving energy is fulfilled by isolating air convection heat transfer between two pieces of glass in vacuum.

The concept of vacuum glass was already proposed by the german physicist Zoller as early as 1913, and the first flat vacuum glass patent in the world was issued in 1924. Vacuum glass samples were produced in the laboratory by Robinson and Collins et al, university of Sydney, 1989, using sealing glass, and edge sealing with vacuum glass at temperatures above 450 ℃. In order to maintain a vacuum space between the two sheets of glass, a square matrix of supports must be provided to withstand about 10 tons of atmospheric pressure per square meter. The supports are key components of vacuum glass products, and the materials of the supports can be glass, ceramics, stainless steel, inconel and the like. In addition, the discharge of the support is also a critical process that determines the efficiency of vacuum glass production.

As a result of research, our country has invented a patent application (CN1168708A) in 1995 relating to vacuum glass supports, which disclose a matrix distribution of supports comprising a core of metallic material and a soft metallic or carbonaceous contact layer at the end thereof. Similarly, an invention patent entitled "vacuum glazing design" filed in 1996 by Tang-Jiang-Zheng et al (TW300271) has a series of support columns disposed between the glass sheets, the support columns including a core made of a high compressive strength material and end portions covered by at least one layer of a soft material. The plum-shaped hydroge, etc. (CN2544066Y) discloses a high thermal insulation and high sound insulation glass with metal wire as support, which is selected from tungsten wire with expansion coefficient close to that of low melting point glass powder. People with appetite or the like (CN201068427Y) discloses a vacuum glass with a multi-layer sealing of an extraction opening by taking microbeads as a support; tangjian (CN201377262Y) discloses a vacuum plate glass support made of metal and having a ring/column structure, and subsequently discloses various shapes of supports with adhesive materials on the surfaces, and the supports are used in vacuum glass (CN 103848557A). Other various supports and corresponding vacuum glass structures or preparation methods also comprise Chinese patents CN105384361A, CN106673461A, CN207685138U, CN108516704A, CN110156347A, CN109369036A, CN109665726A and the like. In summary, in a series of prior art techniques for manufacturing vacuum glass as listed in the above documents, it is generally required to first arrange a support (a columnar structure of high strength metal, ceramic or plastic material, with a diameter of 0.3-0.5mm and a height of about 0.2mm) on the glass, and then arrange a sealing material (low temperature glass frit or low melting point metal, etc.) on the glass. The mode leads to the difficulty in effectively fixing the support arranged in advance, has poor process efficiency and low yield, and greatly restricts the industrial production efficiency of the vacuum glass. In addition, the common metal support in the prior art becomes a thermal bridge between two pieces of glass, and the heat insulation performance of the vacuum glass is obviously reduced; when heating, the contact part of the metal support and the glass can generate local stress, which seriously affects the quality of the vacuum glass.

In conclusion, in the production of vacuum glass, on the one hand, the problem of high-efficiency arrangement of the supports is solved, on the other hand, the problem of material of the supports is solved, and on the third hand, the problems of edge sealing material arrangement, edge sealing efficiency and reliability are solved.

Disclosure of Invention

The invention aims to solve the problems in the prior art and provides a method for preparing vacuum glass by one-step completion of a support and a sealing material, which comprises the following steps: pretreating glass, arranging a support and an edge sealing material on the surface of the glass simultaneously, and drying for later use; covering another piece of pretreated glass to form a hollow layer, transferring the assembled glass into a vacuum heating furnace for vacuum heat treatment, softening the support and the edge sealing material, simultaneously realizing edge sealing and connection and fixation of the support and the glass, and finally cooling to obtain the vacuum glass.

Furthermore, the support and the edge sealing material are made of the same material and are both low-temperature glass powder.

Further, the low-temperature glass powder is made of vanadium-based glass (such as V)₂O₅-ZnO-B₂O₃-R₂O、V₂O₅-P₂O₅-CaO-R₂O、V₂O₅-P₂O₅-Sb₂O₃-R₂O or V₂O₅-TeO₂-SnO₂-R₂O and R are alkali metal elements such as Na and K, the same applies below) by grinding. Preferably, the chemical composition of the low-temperature glass powder is as follows: v₂O₅45％～64％，P₂O₅25％～35％，B₂O₃1％～2％，R₂O1％～4％，TeO ₂3 to 5 percent, and the content of the other components is 1 to 7 percent, and the total is 100 percent. The vanadium-based glass has a transition temperature of 360-^-7/℃。

Furthermore, the low-temperature glass powder is doped with low-expansion glass ceramic powder, and the adding amount of the low-expansion glass ceramic powder is not more than 20% of the mass of the low-temperature glass powder. The main purpose of adding the low-expansion glass-ceramic powder is to adjust the expansion coefficient of the support.

Further, the low-expansion glass-ceramic powder is specifically spodumene-based glass (Li)₂ O 3％～5％，A l₂O₃10％～13％，SiO₂50％～60％，TiO ₂1％～2％，B₂O₃1％～2％，R₂O2% -3%, and the total is 100%).

Further, the glass pretreatment method specifically comprises the following steps: cleaning the glass, and then fully drying the glass in an environment with the temperature of more than 100 ℃.

Further, the supports are arranged on the surface of the glass in an array mode, and the edge sealing materials are continuously arranged along the edge of the glass. The arrangement mode of the support or the edge sealing material is selected from at least one of spraying, 3D printing and screen printing.

Further, the arranged supports are cylindrical, hemispherical or polygonal, the width (or diameter) and height of each support are 0.2-0.5mm, and the spacing distance between every two adjacent supports is 5-50 mm. The width of the arranged edge sealing material is 5-50 mm.

Further, the drying temperature is not lower than 100 ℃ and the drying time is 30-60min after the support and the edge sealing material are arranged.

Further, the heat treatment process of the vacuum heating furnace is as follows: at vacuum degree of not less than 10^-1Under the condition of Pa, the assembled glass is heated to 380-460 ℃ (the temperature is controlled within +/-10 ℃, and the softening temperature of the supporting materials and the edge sealing materials is controlled), and the vacuum degree in the furnace is continuously pumped so that the vacuum degree is not lower than 10^-3Pa for 0.5-1 h,and finally, naturally cooling to room temperature, inflating the furnace to atmospheric pressure, and taking out.

Furthermore, the vacuum glass is flat vacuum glass or arc bending vacuum glass.

Compared with the prior art, the invention has the following beneficial effects: (1) the supports and the edge sealing materials are simultaneously and synchronously distributed on the glass in a printing, printing or spraying mode, so that the subsequent fixing of the supports and the glass and the simultaneous and synchronous edge sealing are facilitated, the working procedures and time are greatly saved, and the production efficiency is improved; (2) the material of the support is basically consistent with that of the glass, and the expansion rate is flexible and adjustable, so that the stress of the contact part of the support and the glass is reduced; (3) an air suction port does not exist during edge sealing, the edge sealing quality and reliability are ensured, and the manufactured vacuum glass product has good heat insulation and sound insulation effects; (4) is particularly suitable for manufacturing arc-shaped vacuum glass and has strong adaptability.

Drawings

FIG. 1 is a schematic structural view of a flat vacuum glass produced in example 1 of the present invention;

FIG. 2 is a cross-sectional view of FIG. 1;

FIG. 3 is a cross-sectional view of an arc-bent vacuum glass manufactured in example 2 of the present invention.

Wherein, the glass comprises 1-upper layer glass, 2-lower layer glass, 3-sealing material, 4-support and 5-hollow layer.

Detailed Description

In order to make those skilled in the art fully understand the technical solutions and advantages of the present invention, the following embodiments are further described.

The vacuum glass is assembled by taking common float glass with the size of 150 multiplied by 70 multiplied by 4 as an example, and the shear strength (or the sealing strength of the glass) of the sealing glass is tested by utilizing a vacuum glass sample with the size of 20 multiplied by 4.

Example 1

And cleaning the common float glass with water, and fully drying for later use. The method is characterized in that low-temperature glass powder (ingredients are shown in the above description) is used as a raw material, and a support and an edge sealing material are simultaneously manufactured on the surface of one piece of glass in a printing mode. The shape of the support is cylindrical, the nominal diameter is 0.3mm, the height is 0.25 or 0.20mm, the distance between every two adjacent supports is 10-20 mm, and the width of the edge sealing material is 5-10 mm. And after the material distribution is finished, transferring the glass into an oven to be dried for 1h at 110 ℃, and covering another piece of glass preheated to the same temperature on the surface of the distributed glass to finish the assembly.

Transferring the assembled two pieces of glass to a vacuum furnace, and vacuumizing to 10 DEG^-2Pa to 110 deg.C, heating to 410 + -10 deg.C, and vacuumizing to 10 deg.C^-4Pa, maintained under the condition for 0.5 h. And after the support and the edge sealing material are softened and sealed, stopping heating to naturally cool the support and the edge sealing material, inflating the furnace to atmospheric pressure, and safely opening the furnace to obtain the flat vacuum glass. The structure of the flat vacuum glass is shown in figure 1-2, and the shear strength of the packaging glass is measured to be 0.22MPa through experiments.

Example 2

This embodiment is substantially the same as embodiment 1 except that: heating the vacuum heating furnace to 410 +/-10 ℃ and vacuumizing to 10 DEG C^-4Pa, maintained under the condition for 1 h. The shear strength of the encapsulating glass was found to be 0.51 MPa.

Example 3

This embodiment is substantially the same as embodiment 1 except that: the raw materials for manufacturing the support and the edge sealing material are a mixture of low-temperature glass powder and the low-expansion glass ceramic powder, and the mixing mass ratio of the low-temperature glass powder to the low-expansion glass ceramic powder is 100: 3; the temperature of the vacuum heating furnace is 420 +/-10 ℃, and the vacuum and heat preservation time is 1 h. The shear strength of the encapsulating glass was found to be 0.87 MPa.

Example 4

This embodiment is substantially the same as embodiment 1 except that: the raw materials for manufacturing the support and the edge sealing material are a mixture of low-temperature glass powder and the low-expansion glass ceramic powder, and the mixing mass ratio of the low-temperature glass powder to the low-expansion glass ceramic powder is 100: 6; the temperature of the vacuum heating furnace is 440 +/-10 ℃, and the vacuum and heat preservation time is 1 h. The shear strength of the encapsulating glass was found to be 1.35 MPa.

Example 5

This embodiment is substantially the same as embodiment 1 except that: the raw materials for manufacturing the support and the edge sealing material are a mixture of low-temperature glass powder and low-expansion glass ceramic powder, and the mixing mass ratio of the low-temperature glass powder to the low-expansion glass ceramic powder is 100: 8; the temperature of the vacuum heating furnace is 460 +/-10 ℃, and the vacuum and heat preservation time is 0.5 h. The shear strength of the encapsulating glass was found to be 1.73 MPa.

Example 6

This embodiment is substantially the same as embodiment 1 except that: the raw materials for manufacturing the support and the edge sealing material are a mixture of low-temperature glass powder and low-expansion glass ceramic powder, and the mixing mass ratio of the low-temperature glass powder to the low-expansion glass ceramic powder is 100: 8; the temperature of the vacuum heating furnace is 460 +/-10 ℃, and the vacuum and heat preservation time is 1 h. The shear strength of the encapsulating glass was experimentally determined to be 2.33 MPa.

Example 7

This embodiment is substantially the same as embodiment 1 except that: the raw materials for manufacturing the support and the edge sealing material are a mixture of low-temperature glass powder and low-expansion glass ceramic powder, and the mixing mass ratio of the low-temperature glass powder to the low-expansion glass ceramic powder is 100: 10; the temperature of the vacuum heating furnace is 460 +/-10 ℃, and the vacuum and heat preservation time is 1 h. The shear strength of the encapsulating glass was experimentally determined to be 2.32 MPa.

Example 8

Several pieces of ordinary float glass with curved surfaces were prepared, and the height of the arch was measured to be 5mm and the horizontal dimension was 150X 70X 4. And cleaning the cambered glass with water, and fully drying for later use. The method comprises the steps of simultaneously manufacturing a support and an edge sealing material on the surface of one piece of cambered glass by using low-temperature glass powder as a raw material in a screen printing mode. The shape of the support is cylindrical, the nominal diameter is 0.3mm, the height is 0.2mm, the distance between two adjacent supports is 20mm, and the width of the edge sealing material is 15 mm. And after the material distribution is finished, transferring the cambered glass into an oven to be dried for 0.5h at 110 ℃, and covering the other piece of cambered glass preheated to the same temperature on the surface of the distributed cambered glass to finish the assembly. Vacuumizing the vacuum heating furnace to 10 DEG^-2Pa to 110 ℃, transferring the assembled cambered surface glass into a vacuum heating furnace, heating to 410 +/-10 ℃, and continuously vacuumizing to 10 DEG C^-4Pa and maintaining for 0.5 h. Stopping heating after the support and the edge sealing material are softened and sealed, naturally cooling to room temperature, inflating the furnace to atmospheric pressure, and safely opening the furnaceObtaining the cambered surface vacuum glass.

Examples 9 to 14

6 kinds of vacuum glasses with different cambered surfaces are prepared by adopting the cambered glass same as the cambered glass in the embodiment 8 and respectively referring to the processes in the embodiments 2 to 7.

The vacuum glass samples prepared in the embodiments are soaked in boiling water for 30-60 minutes and then taken out, the inner surfaces of the glass are observed by naked eyes after the glass samples are cooled and aired, and the result shows that all the inner surfaces of the vacuum glass samples have no water vapor marks, which indicates that the packaging reliability is good.

Claims

1. A vacuum glass preparation method for a supporter and a sealing material to be completed at one time, characterized in that the method comprises the following steps: after the glass is pretreated, the supporter and the edge sealing material are simultaneously arranged on its surface, and dried for later use; Put another piece of pretreated glass to form a hollow layer, transfer the assembled glass into a vacuum heating furnace for vacuum heat treatment, soften the support and the edge sealing material, and realize the connection and fixation of the edge sealing and the support and the glass, and finally cool down That's it.

2 . The preparation method of claim 1 , wherein the support and the edge sealing material are made of the same material, and both are low-temperature glass frit. 3 .

3 . The preparation method according to claim 2 , wherein the low-temperature glass powder is pulverized from vanadium-based glass, and its chemical composition is: V ₂ O ₅ 45%-64%, P ₂ O ₅ 25% ~35%, B ₂ O ₃ 1% ~ 2%, R ₂ O 1% ~ 4%, TeO ₂ 3% ~ 5%, and the rest of the components are 1% ~ 7%; the transition temperature of the vanadium glass is 360-407℃, the expansion coefficient is (86.5～89.9)×10 ^-7 /℃.

4. The preparation method according to claim 2, characterized in that: low-expansion glass-ceramic powder is also added to the low-temperature glass powder used as a support and an edge-sealing material, and the added amount does not exceed the quality of the low-temperature glass powder. 20%.

5 . The preparation method according to claim 4 , wherein the low-expansion glass-ceramic powder is specifically spodumene glass, the composition of which is: Li ₂ O 3% to 5%, Al ₂ O ₃ 10 . %～13%, SiO ₂ 50%～60%, TiO ₂ 1%～2%, B ₂ O ₃ 1%～2%, R ₂ O 2%～3%, R is selected from Na or K.

6. The preparation method according to claim 1, characterized in that: the glass is cleaned first during pretreatment, and then placed in an environment above 100°C to be fully dried; The drying temperature is not lower than 100℃, and the drying time is 30-60min.

7 . The preparation method according to claim 1 , wherein the support is arranged on the glass surface by spraying, 3D printing or screen printing to form a support matrix, and the edge sealing material is continuously arranged along the edge of the glass. 8 . .

8. The preparation method according to claim 7, wherein the arranged supports are cylindrical, hemispherical or polygonal, and the width, diameter and height are 0.2-0.5mm, and two adjacent supports The distance between them is 5-50mm, and the width of the edge banding material is 5-50mm.

9. preparation method as claimed in claim 1 is characterized in that: vacuum heating furnace heat treatment process is specifically as follows: under the situation that vacuum degree is not less than 10 ^-1 Pa, the assembled glass is heated to 380-460 ℃, Continue to evacuate so that the vacuum degree in the furnace is not lower than 10 ^-3 Pa and maintain for 0.5 to 1 hour, and finally cool to room temperature naturally and inflate the furnace to atmospheric pressure, then take it out.

10 . The preparation method according to claim 1 , wherein the vacuum glass is flat vacuum glass or curved vacuum glass. 11 .