WO2018196333A1

WO2018196333A1 - Method for activating built-in getter of vacuum glass

Info

Publication number: WO2018196333A1
Application number: PCT/CN2017/110306
Authority: WO
Inventors: 赵雁; 李彦兵; 王章生; 李素真; 张红霞
Original assignee: 洛阳兰迪玻璃机器股份有限公司
Priority date: 2017-04-26
Filing date: 2017-11-10
Publication date: 2018-11-01
Also published as: CN107098603A; CN107098603B

Abstract

Disclosed is a method for activating a built-in getter of a vacuum glass, wherein the vacuum glass comprises at least two glass substrates; and a getter is provided in a vacuum layer between the two adjacent glass substrates. In a manufacturing process of the vacuum glass, the adjacent glass substrates are spaced via a supporter to form a vacuum glass member. In the process of manufacturing the vacuum glass, the getter in a vacuum environment is preheated, and the preheating temperature is 100-300 degrees centigrade lower than an activation temperature of the getter, and the preheating lasts for 153 seconds to 603 seconds; then the vacuumization of the vacuum environment is maintained; and then the getter is activated before or after the vacuum glass member is sealed. The method effectively improves air suction performance of the getter, allowing the manufactured vacuum glass to have a very high initial vacuum degree, and prolongs the service life of the vacuum glass.

Description

Activation method of built-in getter for vacuum glass

Technical field

The invention relates to the field of vacuum glass technology, in particular to a method for activating a getter in a vacuum glass.

Background technique

The excellent performance of vacuum glass depends to a large extent on the vacuum layer between the two sheets of glass. To ensure the full performance of the vacuum glass, the maintenance of the vacuum is crucial. Due to the surface deflation of the glass and the edge-sealing material and the inherent gas permeability of the constituent materials of the vacuum glass, the vacuum glass will exhibit a vacuum attenuation phenomenon during long-term use. In order to maintain the vacuum of the vacuum glass vacuum layer, it is usually necessary to place a getter in the vacuum layer.

A getter, also known as a getter, is used in vacuum electronics and other vacuum technologies. It is a material that absorbs residual gases and water vapor and a fixed atmosphere. In the vacuum glass, the main function of the getter is to absorb the residual gas in or after the vacuum glass cavity, and improve the vacuum in the cavity to ensure a good vacuum state, prolong the service life and improve the reliability of the vacuum glass. .

The fresh metal surface of the getter is in contact with the atmosphere, and physical adsorption and chemical adsorption occur simultaneously. In a short time, a single layer of chemical adsorption layer is formed on the surface of the getter. At normal temperature, in the initial reaction stage, the surface vacancies of the getter portion are occupied by gas molecules, forming weak chemical adsorption (molecular state adsorption), and the adsorption is reversible. Over time, the thermodynamic effect will gradually manifest itself. The weakly chemically adsorbed molecules will be gradually replaced by dissociative adsorption products (atoms) such as water vapor, oxygen, carbon monoxide, etc., forming stable strong chemical adsorption (dissociative adsorption or atomic adsorption). ), and with weak chemical adsorption gradually tend to thermodynamic equilibrium. At normal temperatures, the ability of these atoms to diffuse inside the getter material is very weak, causing these atoms to be distributed primarily on the surface of the getter material and preventing the getter material from continuing to inhale.

The getter must be activated before it fully exerts its sorption effect on the convective reactive gas. The usual activation method is to heat the getter to a certain temperature to eliminate the surface passivation layer, thereby achieving the activation purpose. In the field of vacuum glass technology, getters are usually activated after vacuum glass processing is completed.

However, according to the prior method, the vacuum glass produced by directly activating the getter in the vacuum glass vacuum layer has the following defects: 1. The gas molecules adsorbed on the surface of the getter are released into the vacuum layer, which is somewhat reduced. The vacuum degree of the vacuum layer causes the heat transfer coefficient of the vacuum glass to be high, and even falls short of the requirements of the qualified product, and is directly scrapped; 2. During the later use of the vacuum glass, the gas molecules released from the surface of the getter will be sucked again. The gas agent adsorbs, thereby reducing the gettering capacity of the getter, resulting in a decrease in the vacuum degree of the vacuum glass and a decrease in the life, as shown in FIG.

Summary of the invention

In view of the problems existing in the prior art, an object of the present invention is to provide a vacuum glass getter The activation method effectively improves the gettering performance of the getter, and the vacuum glass produced has a very high initial vacuum and improves the service life of the vacuum glass.

In order to achieve the above object, the technical solution of the present invention is as follows:

A method for activating a getter in a vacuum glass, the vacuum glass comprising at least two glass substrates, wherein a vacuum layer is disposed in a vacuum layer between two adjacent glass substrates, and in the vacuum glass manufacturing process, the phase is The adjacent glass substrates are separated by a support to form a vacuum glass member. During the process of fabricating the vacuum glass, the getter in a vacuum environment is preheated, and the preheating temperature is lower than the activation temperature by 100 ° C to 300 ° C. The duration of the heating is from 153 seconds to 603 seconds; then, the vacuum environment is kept under vacuum; after that, the getter is activated before or after the vacuum glass member is sealed.

Further, the getter has an activation temperature of 500 ° C to 600 ° C, and the getter has a preheating temperature of 273 ° C to 428 ° C.

Further, when the glass substrate has an air suction port, the specific steps are:

Step 1) sealing the periphery of the vacuum glass member;

Step 2), vacuuming the sealed vacuum glass member from the air suction port;

Step 3), preheating the getter;

Step 4), maintaining a vacuum on the sealed vacuum glass member, closing the suction port and activating the getter;

The process of closing the suction port and activating the getter can be performed in one of the following ways:

a. sealing the suction port on the sealed vacuum glass member, and then heating the getter to activate the temperature to activate the getter;

b. Heating the getter to the activation temperature to activate the getter, and then closing the suction port on the sealed vacuum glass member.

Further, when there is no air suction port on the glass substrate, the specific steps are:

Step 1), placing the vacuum glass member into a vacuum chamber having a certain vacuum environment;

Step 2), preheating the getter disposed in the vacuum glass member;

Step 3), maintaining a vacuum in the vacuum chamber, sealing the periphery of the vacuum glass member and activating the getter;

The process of sealing and activating the getter around the vacuum glass member can be performed in one of the following ways:

a. sealing the periphery of the vacuum glass member, and then heating the getter to activate the temperature to activate the getter;

b. Heating the getter to the activation temperature to activate the getter, and then sealing the periphery of the vacuum glass member.

Further, the vacuum environment has a degree of vacuum of from 1 × 10 ^-1 Pa to 1 × 10 ^-7 Pa.

Further, the getter continues to evacuate the vacuum environment in which it is subjected to preheating.

Further, the heating method of the preheating is microwave heating, laser heating or induction heating.

Further, the laser used for the laser heating is an infrared laser.

Further, the getter is a non-evaporable getter.

In the vacuum glass manufacturing process, by the method of the invention, the getter is preheated to remove the gas adsorbed on the surface of the getter before the getter is activated, thereby effectively reducing or avoiding the release of gas molecules during the activation of the getter and again The gas molecules released by the adsorption ensure the getter capacity after the getter is activated, and improve the normal temperature gettering performance after the getter is activated; thereby, the initial vacuum degree and the later service life of the vacuum glass can be significantly improved.

DRAWINGS

Figure 1 is a diagram showing the change in the degree of vacuum of a vacuum glass directly activating a getter according to the prior art;

Figure 2 is a diagram showing the change in the degree of vacuum of the vacuum glass using the getter activated by the present invention;

Figure 3 is a gassing curve of the getter at 300 ° C;

Figure 4 is a gassing curve of the getter at 350 ° C;

Figure 5 shows the venting profile of the getter at 400 °C.

detailed description

The technical solutions of the present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.

Example 1

The vacuum glass comprises at least two glass substrates, wherein one glass substrate is provided with an air suction port, and a vacuum layer is disposed in a vacuum layer between two adjacent glass substrates, and in the vacuum glass manufacturing process, adjacent glass substrates are disposed. A vacuum glass member is formed by the spacer spacing. Before vacuuming the vacuum glass member, the periphery of the vacuum glass member is sealed, so that the vacuum layer is connected to the external environment only through the suction port, and the vacuum pump is connected with the suction port to evacuate the sealed vacuum glass member; When the degree of vacuum reaches 1×10 ^-1 Pa to 1×10 ^-7 Pa, the vacuum is heated, and the getter in the vacuum layer is preheated by heating by microwave heating, laser heating or induction heating. The preheating temperature should be lower than the activation temperature of the getter 100 ° C -300 ° C, the preferred preheating temperature is 273 ° C to 428 ° C, the duration is 153 s to 603 s, for example: when using laser heating, the wavelength is 780 nm Heating to an infrared laser of 1400 nm, preferably at a wavelength of 980 nm; after vacuuming the sealed vacuum glass member to a vacuum degree, the suction port is closed to complete the sealing of the vacuum glass; heating the getter The getter is activated to an activation temperature of 500 ° C to 600 ° C, and the same heating method as preheating can be used.

The getter may be an evapotranspiration getter or a non-evaporable getter. When a non-evaporable getter is used, it includes: Zr, Ti, Nb, Ta or V and alloys thereof. The getter in this embodiment is preferably a zirconium vanadium iron getter.

Principle analysis:

The vacuum glass is evacuated to a high vacuum state, and the molecular molecules adsorbed in the molecular state can be desorbed under low temperature and long time dynamic high vacuum conditions, and a certain amount of surface active vacancies are formed on the surface of the getter.

Surface active vacancies cannot be produced by desorption under vacuum conditions after strong chemical adsorption.

H ₂ O, CO, CO ₂ , O ₂ , N ₂ and the like are permanently absorbed. The chemical bonds of the reactive gas molecules form oxides, carbides and nitrides in the atomic form with the getter material after the surface of the getter has broken. At ordinary temperatures, the ability of these atoms to diffuse inside the getter material is very weak, causing these atoms to be mainly distributed on the surface of the getter material. Heating can effectively eliminate the gas molecules adsorbed on the surface of the getter.

After heating, the gas molecules adsorbed on the surface of the getter are desorbed into the vacuum layer of the vacuum glass and discharged with the vacuum process.

The getter is activated after a vacuum of 20-25 min and the vacuum is as low as the pre-heating vacuum. H ₂ is reversible absorption. The diffusion of hydrogen into the interior of the getter material is rapid and is stored in the getter alloy in the form of a solid solution. After the pre-heated getter surface adsorbs most of the desorbed gas and releases the vacuum glass vacuum layer, the internal solid solution of H _{2 is} released when the getter is activated.

2 and FIG. 1 can be seen that the initial vacuum of the vacuum glass prepared according to the activation method of the present invention is higher, and the degree of vacuum changes smoothly with the passage of time, and the degree of vacuum in FIG. 1 does not appear. Happening.

3, FIG. 4 and FIG. 5 are the inventors investigating the effect of preheating temperature on the desorption of adsorbed gas on the surface of the getter. For this reason, the inventors conducted a large number of experiments to study the outgassing of the getter at different heating temperatures. Graph. 3 is a venting curve of the getter at a preheating temperature of 300 ° C, FIG. 4 is a venting curve of the getter at a heating temperature of 350 ° C, and FIG. 5 is a venting curve of the getter at a heating temperature of 400 ° C. It can be seen that as the preheating temperature continues to increase, the "peak" of the curve is also increasing, reflecting two phenomena: 1. Heating the getter before activation, the gas molecules on the surface of the getter can be After desorption, it is decomposed into a free gas molecule and released into the vacuum layer of the vacuum glass. 2. As the heating temperature increases, the desorption effect of the gas molecules is more pronounced, and the "peak" of the curve is higher.

Experimental studies have shown that, below the heating temperature of 273 ° C, the phenomenon that the gas adsorbed on the surface of the getter is decomposed into free gas molecules is not obvious, and even cannot be decomposed; and the getter is activated when the heating temperature is higher than 428 ° C or Partially activated.

Example 2

The vacuum glass comprises at least two glass substrates, wherein one glass substrate is provided with an air suction port, and a vacuum layer is disposed in a vacuum layer between two adjacent glass substrates, and in the vacuum glass manufacturing process, adjacent glass substrates are disposed. A vacuum glass member is formed by the spacer spacing. Before vacuuming the vacuum glass member, the periphery of the vacuum glass member is sealed, so that the vacuum layer is connected to the external environment only through the suction port, and the vacuum pump is connected with the suction port to evacuate the vacuum layer; the vacuum degree in the vacuum layer is 1 When the temperature is from 10 to ¹ Pa to 1 × 10 ^-7 Pa, the suction agent in the vacuum layer is preheated by the heating method such as microwave heating, laser heating or induction heating while continuously evacuating, and the temperature of the preheating is performed. It should be lower than the activation temperature of the getter 100 ° C to 300 ° C, the preferred preheating temperature is 273 ° C to 428 ° C, the duration is 153 s to 603 s; vacuuming the sealed vacuum glass member to achieve vacuum After setting the degree of vacuum, the getter is heated to an activation temperature of 500 ° C to 600 ° C to activate the getter. At this time, the same heating method as that of the preheating can be used; then the suction port is closed to complete the sealing of the vacuum glass.

Example 3

The vacuum glass comprises at least two glass substrates, and a getter is disposed in a vacuum layer between two adjacent glass substrates. In the process of manufacturing the vacuum glass, adjacent glass substrates are separated by a support to form a vacuum glass member. . In the embodiment, the glass substrate is not provided with an air suction port, and the vacuum glass member is placed in a vacuum chamber (vacuum environment), and the vacuum chamber is evacuated by a vacuum pump to maintain the vacuum degree of the vacuum chamber at 1×10 ^-1 Pa. Between 1×10 ^-7 Pa, the getter placed in the vacuum glass member is preheated, and the getter is preheated by a heating method such as microwave heating, laser heating or induction heating, and the temperature of the preheating is performed. It should be lower than the activation temperature of the getter 100 ° C to 300 ° C, the preferred preheating temperature is 273 ° C to 428 ° C, the duration is 153 s to 603 s; after the vacuum in the vacuum chamber reaches the set vacuum degree, The periphery of the vacuum glass member is sealed to complete the sealing of the vacuum glass; then the getter is heated to an activation temperature of 500 ° C to 600 ° C to activate the getter.

Example 4

This embodiment is basically the same as the activation method of Embodiment 3, except that after preheating the getter, the getter is heated to an activation temperature of 500 ° C to 600 ° C to activate the getter; and then, to be vacuumed After the vacuum degree in the room reaches the set vacuum degree, the periphery of the vacuum glass member is sealed to complete the sealing of the vacuum glass.

The above description of the preferred embodiments of the present application has been described with reference to the accompanying drawings, but the present application is not limited thereto, and any modifications and/or variations made by those skilled in the art without departing from the spirit of the present application belong to The scope of protection of this application.

Claims

A method for activating a getter in a vacuum glass, the vacuum glass comprising at least two glass substrates, wherein a vacuum layer is disposed in a vacuum layer between two adjacent glass substrates, and in the vacuum glass manufacturing process, the phase is The adjacent glass substrates are separated by a support to form a vacuum glass member, characterized in that in the process of manufacturing the vacuum glass, the getter in a vacuum environment is preheated, and the preheating temperature is lower than the activation temperature by 100 ° C to At 300 ° C, the preheating duration is from 153 seconds to 603 seconds; then, the vacuum environment is kept under vacuum; after that, the getter is activated before or after the vacuum glass member is sealed.
The activation method according to claim 1, wherein the getter has an activation temperature of 500 ° C to 600 ° C and the getter has a preheating temperature of 273 ° C to 428 ° C.
The activation method according to claim 1 or 2, wherein when the glass substrate has an air suction port, the specific steps are:

Step 1) sealing the periphery of the vacuum glass member;

Step 2), vacuuming the sealed vacuum glass member from the air suction port;

Step 3), preheating the getter;

Step 4), maintaining a vacuum on the sealed vacuum glass member, closing the suction port and activating the getter;

The process of closing the suction port and activating the getter can be performed in one of the following ways:

a. sealing the suction port on the sealed vacuum glass member, and then heating the getter to activate the temperature to activate the getter;

b. Heating the getter to the activation temperature to activate the getter, and then closing the suction port on the sealed vacuum glass member.
The activation method according to claim 1 or 2, wherein when there is no suction port on the glass substrate, the specific steps are:

Step 1), placing the vacuum glass member into a vacuum chamber having a certain vacuum environment;

Step 2), preheating the getter disposed in the vacuum glass member;

Step 3), maintaining a vacuum in the vacuum chamber, sealing the periphery of the vacuum glass member and activating the getter;

The process of sealing and activating the getter around the vacuum glass member can be performed in one of the following ways:

a. sealing the periphery of the vacuum glass member, and then heating the getter to activate the temperature to activate the getter;

b. Heating the getter to the activation temperature to activate the getter, and then sealing the periphery of the vacuum glass member.
The activation method according to claim 1, wherein the vacuum atmosphere has a degree of vacuum of from 1 × 10 -1 Pa to 1 × 10 -7 Pa.
The activation method according to claim 1, wherein said getter continues to evacuate a vacuum environment in which it is subjected to preheating.
The activation method according to claim 1, wherein the preheating heating mode is microwave heating, laser heating or induction heating.
The activation method according to claim 7, wherein the laser light used for the laser heating is an infrared laser.
The activation method according to claim 1, wherein the getter is a non-evaporable getter.