Composite getter material capable of efficiently absorbing nitrogen, and preparation method therefor

Abstract

The present invention relates to the field of new materials. Disclosed are a composite getter material capable of efficiently absorbing nitrogen, and a preparation method therefor. The composite getter material comprises a main component A and an additive component B. The main component A and the additive component B form an aAbB composite getter, wherein a+b=100%, 50 wt%≤a<100 wt%, and 0 wt%<b<50 wt%. The composition of the main component A is (SiO2)1-x-y-z(Al2O3)x(CaO)yCz, wherein 20 wt%≤x≤70 wt%, 10 wt%≤y≤60 wt%, and 0 wt%≤z≤40 wt%. The additive component B is a metal compound Zr-Ti-V getter material. The aAbB composite getter of the present invention has greatly improved absorption capacity for CO and H2O; moreover, the getter material can also absorb N2 on the basis of absorbing CO and H2O, thereby ameliorating the problem of existing metal oxides having poor N2 absorption capacity, and also improving the absorption capacity of the metal oxide (SiO2)1-x-y-z(Al2O3)x(CaO)yCz for CO, H2O and N2.

Description

Composite getter material with high nitrogen absorption efficiency and preparation method thereof TECHNICAL FIELD

[0001] The present application relates to the field of new materials, in particular to a composite getter material with high nitrogen absorption efficiency and a preparation method thereof. BACKGROUND

[0002] In modern industry, scientific research and daily life, efficient and stable getter materials are crucial for maintaining the gas purity and low pressure environment in a closed system (such as vacuum equipment, gas storage containers, electronic device packaging, etc.). Traditional metal oxide getter materials are widely used due to their good absorption performance for specific gases (such as CO and H2O). However, these materials often show insufficient absorption capacity for inert gases such as N2, which limits their application in situations where multiple gas components need to be controlled.

[0003] Existing getter materials have abundant active sites on their surfaces, which can effectively adsorb and fix polar molecules such as CO and H2O. For example, metal oxides (SiO2) 1-x-y-z (Al2O3) x (CaO) y C z Getter materials are prepared by mixing metal oxides SiO2, Al2O3, CaO, and activated carbon powder in a certain proportion, which can effectively absorb CO and H2O. When applied in CO and H2O impurity-containing gas or vacuum environment, it can effectively remove impurity gases and achieve the effect of purifying gas or removing CO and H2O in the vacuum environment.

[0004] However, for non-polar N2 molecules, the adsorption efficiency of metal oxides is significantly reduced due to the lack of effective interaction mechanisms. Although current metal oxide (SiO2) 1-x-y-z (Al2O3) x (CaO) y C z Getters are widely used and can effectively remove impurity H2O or CO in gas, but the impurity gas in gas is generally diversified, such as N2. If N2 is to be absorbed, the current (SiO2) 1-x-y-z (Al2O3) x (CaO) y C z Getter cannot solve this problem. SUMMARY

[0005] The main purpose of the present application is to solve the technical problem of low adsorption efficiency of non-polar N2 molecules in the prior art. A composite getter material with high nitrogen absorption efficiency, comprising a main component A and an additive component B, the main component A and the additive component B form an aAbB composite getter, wherein a+b=100%; 50wt%≤a<100wt%; 0wt%<b<50wt%; the components of the main component A are: (SiO2) 1-x-y-z (Al2O3) x (CaO) y C z , wherein 20wt%≤x≤70wt%; 10wt%≤y≤60wt%; 0wt%≤z≤40wt%; the additive component B is a metal compound Zr-Ti-V getter material.

[0006] The main component A is a powder with a particle size of 3-5nm. The additive component B is a powder with a particle size of 8-50 microns. In the aAbB composite getter, 60wt%≤a≤95wt%; 1wt%≤b≤40wt%.

[0007] The second aspect of the present application provides a preparation method of a composite getter material with high nitrogen absorption efficiency, comprising the following steps:

[0008] Different contents of SiO2, Al2O3, CaO, activated carbon C powder with a powder particle size of 70-230μm are put into a ball mill of model XXX for ball milling, the alcohol added during ball milling is 5%-15%, zirconia balls are used during ball milling, the diameter of the balls is XX-XXmm, the ball-to-material ratio is 1-3, and the ball milling time is 5-10 hours. The (SiO2) 1-x-y-z (Al2O3) x (CaO) y C z , wherein 20wt%≤x≤70wt%; 10wt%≤y≤60wt%; 0wt%≤z≤40wt%.), into a ball mill of model XXX for ball milling, the alcohol added during ball milling is 5%-15%, zirconia balls are used during ball milling, the diameter of the balls is XX-XXmm, the ball-to-material ratio is 1-3, and the ball milling time is 5-10 hours. The (SiO2) 1-x-y-z (Al2O3) x (CaO) y C z , wherein 20wt%≤x≤70wt%; 10wt%≤y≤60wt%; 0wt%≤z≤40wt%.), into a ball mill of model XXX for ball milling, the alcohol added during ball milling is 5%-15%, zirconia balls are used during ball milling, the diameter of the balls is XX-XXmm, the ball-to-material ratio is 1-3, and the ball milling time is 5-10 hours. The (SiO2)

[0009] Preparation of Zr-Ti-V metal compound getter material additive component B: ①Pure Zr, Ti and V elements with purity of 99.9% are prepared according to the formula of Zr 43.49 Ti 2.54 V 53.97 wt%. ②The prepared raw materials are sequentially placed in the copper crucible of a smelting furnace according to the order of melting point from low to high, and then the smelting furnace is vacuumized to (1-5) × 10 -3 Pa, and then high-purity argon with purity of 99.9999% is introduced to wash the furnace, and then the smelting furnace is vacuumized to (1-5) × 10 -3 Pa again. ③Then the alloy is smelted under an argon atmosphere with a pressure of 0.05 MPa. A CZL-300 type vacuum magnetic tungsten electrode arc furnace is used for smelting. The power supply for arc smelting is turned on, and the arc is started on the tungsten electrode, and then the arc is stabilized and smelting is performed on the titanium ingot. During smelting, the smelting current is about 80-220 A. The Zr 43.49 Ti 2.54 V 53.97 alloy is completely smelted and cast into an ingot. In order to ensure the uniformity of the Ti 2.54 V 53.97 alloy, the entire smelting process needs to be smelted for 4 times, and after each smelting is completed, the Ti 2.54 V 53.97 alloy ingot is turned over by a mechanical arm and smelted for 4 times again until it is uniform.

[0010] The smelted alloy is broken and ball milled under an Ar or N2 atmosphere, the pressure of the protective atmosphere is 0.04-0.2 MPa, and the ball milling time is 2-10 h. The powder is ball milled to 270 mesh (50 μm)-1800 mesh (8 μm), and the powder with a particle size of 8-50 μm forms the additive component B.

[0011] The main component A and the additive component B are physically mixed to form aAbB components, and the composite getter is prepared, wherein 60 wt%≤a≤95 wt%; 1 wt%≤b≤40 wt%.

[0012] The present application has the following beneficial effects:

[0013] The getter material of the present application not only greatly improves the absorption capacity of CO and H2O, but also can absorb N2 at the same time on the basis of absorbing CO and H2O. The problem of poor N2 absorption capacity of existing metal oxides is improved, and the absorption capacity of CO, H2O and N2 of the metal oxides (SiO2) 1-x-y-z (Al2O3) x (CaO) y C z is improved. BRIEF DESCRIPTION OF DRAWINGS

[0014] Fig. 1 is a schematic diagram of physical adsorption and chemical adsorption. DETAILED DESCRIPTION

[0015] The terms "first", "second", "third", "fourth" and the like in the description and claims of the present application, and above accompanying drawings, if any, are used for distinguishing between similar objects and not necessarily for describing a particular sequential or chronological order. It is to be understood that the use of the terms so construed herein is merely for convenience and brevity and nothing in this application is to be taken as an admission that the application is intended to be limited to this specific order. Furthermore, the terms "comprise", "comprising", "include", "including", and the like are to be construed open-ended, i.e., to mean "including, but not limited to", unless otherwise noted. It is intended that the application encompassing the recited steps or elements can consist of additional steps or elements beyond those listed.

[0016] For the purpose of facilitating understanding, the specific flow of the embodiments of the present application is described as follows. An embodiment of a composite getter material with high nitrogen absorption efficiency in the embodiments of the present application comprises:

[0017] a main component A and an additive component B, the main component A and the additive component B form an aAbB composite getter, wherein a+b=100%; 50wt%≤a<100wt%; 0wt%<b<50wt%;

[0018] The components of the main component A are: (SiO2) 1-x-y-z (Al2O3) x (CaO) y C z wherein 20wt%≤x≤70wt%; 10wt%≤y≤60wt%; 0wt%≤z≤40wt%; the additive component B is a metal compound Zr-Ti-V getter material.

[0019] As a preferred embodiment, the main component A is a powder with a particle size of 3-5 nm. As a preferred embodiment, the additive component B is a powder with a particle size of 8-50 microns. As a preferred embodiment, in the aAbB composite getter, 60wt%≤a≤95wt%; 1wt%≤b≤40wt%.

[0020] The second aspect of the present application provides a preparation method of a composite getter material with high nitrogen absorption efficiency, comprising the following steps:

[0021] Different contents of SiO2, Al2O3, CaO, and activated carbon C powder with a particle size composition of 70-230 μm are mixed according to (SiO2) 1-x-y-z (Al2O3) x (CaO) y C zThe component ratio (wherein 20wt%≤x≤70wt%; 10wt%≤y≤60wt%; 0wt%≤z≤40wt%) is put into a ball mill for ball milling, alcohol is added at 5%-15% during ball milling, zirconium oxide balls are used for ball milling, the diameter of the balls is 0.1-300mm, the ball-to-material ratio is 1-3, and the ball milling time is 5-10 hours. (SiO2) powder with a particle size of 3-5nm is obtained 1-x-y-z (Al2O3) x (CaO) y C z The mixed powder is named as main component A.

[0022] Preparation of Zr-Ti-V metal compound getter material additive component B: ①Purity 99.9% Zr, Ti, V elements are prepared according to the mass ratio of Zr 43.49 Ti 2.54 V 53.97wt%. ②The prepared raw materials are sequentially put into the copper crucible of the smelting furnace in the order of low melting point to high melting point, and then the smelting furnace is vacuumized to (1-5) × 10 -3 Pa, then high-purity argon gas with a purity of 99.9999% is introduced to wash the furnace, and then the vacuum is again extracted to (1-5) × 10 -3 Pa. ③Then the alloy is melted under an argon atmosphere of 0.05MPa. A CZL-300 type vacuum magnetic control tungsten electrode arc furnace is used for smelting. The power supply for arc smelting is turned on, the arc is started on the tungsten electrode, and then the arc is stabilized and smelting is performed on the titanium ingot. During smelting, the smelting current is about 80-220A. The Zr 43.49 Ti 2.54 V 53.97 alloy is completely smelted and cast into an ingot. In order to ensure the uniformity of the Ti 2.54 V 53.97 alloy, the entire smelting process needs to be smelted for 4 times, and after each smelting is completed, the Ti 2.54 V 53.97 alloy ingot is turned over with a mechanical arm and smelted for another 4 times until it is uniform.

[0023] The smelted alloy is crushed and ball milled under an Ar or N2 atmosphere, the pressure of the protective atmosphere is 0.04-0.2MPa, and the ball milling time is 2-10h. The powder is ball milled to 270-1800 mesh, 8-50 microns of powder, forming additive component B.

[0024] The main component A and the additive component B are physically mixed according to aAbB components, and the composite getter is prepared, wherein 60wt%≤a≤95wt%; 1wt%≤b≤40wt%.

[0025] The present invention is based on the current metal oxide getter (SiO2) 1-x-y-z (Al2O3) x (CaO) y C z (wherein 20wt%≤x≤70wt%; 10wt%≤y≤60wt%; 0wt%≤z≤40wt%.), these metal oxides SiO2, Al2O3, CaO, C are mixed in the ratio (SiO2) 1-x-y-z (Al2O3) x (CaO) y C z proportion (wherein 20wt%≤x≤70wt%; 10wt%≤y≤60wt%; 0wt%≤z≤40wt.%) and by the ball milling method, nano-treatment is carried out to be a powder with a powder particle size of 3-5nm. In this application, (SiO2) 1-x-y-z (Al2O3) x (CaO) y C z is named as the main component A.

[0026] In the main component A with a size of 3-5nm, i.e. in (SiO2) 1-x-y-z (Al2O3) x (CaO) y C z metal compound Ti-Zr-V powder is added to the powder, the metal compound Ti-Zr-V powder is named as the additive component B, the particle size of the additive component B powder is 8-50 microns, forming a composite getter aAbB, a[(SiO2) 1-x-y-z (Al2O3) x (CaO) y C z ]b(TiZrV) (aAbB, wherein a+b=100%, 60wt%≤a≤95wt%; 1wt%≤b≤40wt%). Among them, the composite getter not only has the functions of absorbing CO and H2O, but also has the function of absorbing N2.

[0027] As shown in Figure 1, in the main component A oxide (SiO2) 1-x-y-z (Al2O3) x (CaO) y C zWhen the additive component B is added, the 3d electron orbits of Ti, Zr and V in the compound powder interact with the C-O in the CO gas, the H-O in the H2O gas and the N-N in the N2 gas, and change the CO gas molecules, H2O gas molecules and N2 gas molecules in the gas molecules into C, H and N atoms. Since the radii of the C, H and N atoms in the CO, H2O and N2 gas are much smaller than the radii of the gas molecules, the metal compound Ti-Zr-V getter has the function of dissociating the gas molecules into small-atom-radius C, H and N atoms. At the same time, the small-atom-radius can quickly diffuse to the composite getter aAbB, a[(SiO2) 1-x-y-z (Al2O3) x (CaO) y C z ]b(TiZrV) to improve the gettering rate.

[0028] When no metal compound is added, the adsorption force between the metal oxide and the gas molecules is only the Van der Waals force, and the metal oxide cannot dissociate the hydrogen molecules in N2 into N atoms. However, the metal compound Ti-Zr-V can more effectively dissociate the N2 molecules into N-N atoms. Therefore, when the metal compound Ti-Zr-V getter additive component B is added to the main component A of the metal oxide (SiO2) 1-x-y-z (Al2O3) x (CaO) y C z , the composite getter aAbB is formed, that is, a[(SiO2) 1-x-y-z (Al2O3) x (CaO) y C z ]b(TiZrV). The principle of absorbing gas is not only the Van der Waals force between the gas molecules and the composite getter, but also the adsorption of the chemical bond between the atoms and the composite getter, which greatly increases the absorption capacity of the composite getter and enables the composite getter to have the absorption capacity for nitrogen.

[0029] The second aspect of the present application provides a preparation method of a composite getter material with high-efficiency absorption for nitrogen. For details, see Examples 1-10.

[0030] Example 1: For the oxide getter with 100% of the main component A and 0% of the additive component B, the preparation steps are as follows:

[0031] 1) 55% SiO2 powder, 25% Al2O3 powder, 20% CaO powder, and 5% activated carbon powder were mixed. The average particle size of these four powders was 72 μm. They were ball-milled in a KF-4L ball mill with 6% alcohol added. Zirconia balls were used for the milling process, and the milling time was 5.5 hours, yielding a powder with an average particle size of 3.8 nm, and the sample from Example 1. (55% SiO2, 20% Al2O3, 20% CaO, 5% C) The powder had a specific surface area of ​​735 m². 2 / g. This sample has a fidelity of 5×10⁻⁶. -4 Activated at 500℃ for 20 min, the absorption capacity of CO gas at room temperature is 55 ml / s. 2 The nitrogen absorption rate is 0. The specific component ratio, powder particle size, and absorption performance of Example 1 are shown in Table 1.

[0032] Example 2, wherein the main component A is 88% and the added component B is 12%, the preparation steps are as follows:

[0033] 2) 55% SiO2 powder, 25% Al2O3 powder, 20% CaO powder, and 5% activated carbon powder were mixed. The average particle size of the four powders was 75 μm. They were then ball-milled in a KF-4L ball mill with 6.2% alcohol added. Zirconia balls were used for the milling process, and the milling time was 8 hours. The resulting powder had an average particle size of 3.1 nm, which is component A.

[0034] 3) Preparation of the BZr-Ti-V metal compound getter material: ① Zr, Ti, and V elements with a purity of 99.9% were prepared according to a mass ratio of Zr 43.49 wt%, Ti 2.54 wt%, and V 53.97 wt%. ② The prepared raw materials were placed into the copper crucible of the smelting furnace in order of increasing melting point, and then the smelting furnace was evacuated to a vacuum of 2 × 10⁻⁶. -3 Pa, then purging with 99.9999% high-purity argon gas to clean the furnace, and then evacuating to a vacuum of 2.3 × 10⁻⁶ Pa. -3Pa. ③ Then melt the alloy under 0.05 MPa argon atmosphere. The vacuum magnetic control tungsten electrode arc furnace of CZL-300 type is used for melting. The arc power is turned on, and the arc is ignited on the tungsten electrode, then the arc is stabilized and the alloy is melted on the titanium ingot. The melting current is about 90 A. The Zr 43.49 Ti 2.54 V 53.97 alloy is completely melted and cast into ingot. In order to ensure the homogeneity of the Ti 2.54 V 53.97 alloy, the whole melting process needs to be melted for 4 times. After the Ti 2.54 V 53.97 alloy ingot is cooled completely, it is turned over by a mechanical arm and melted for 4 times again until it is homogeneous. ④ The melted alloy is crushed and ball milled under the protection of Ar atmosphere. The pressure of the protection atmosphere is 0.08 MPa, and the ball milling time is 3 h. The powder is ball milled to an average particle size of 30 μm to form the additive component B powder.

[0035] 4) 88% of the main component A and 12% of the additive component B are physically mixed to prepare an 88A12B composite powder getter, and the specific surface area of the powder is 643 m 2 / g. In this example 2, the activation is carried out at a vacuum degree of 4.9 x 10 -4 Pa and a temperature of 250°C for 20 min, and the CO gas absorption performance at room temperature is 54 ml / s.cm 2 , and the nitrogen absorption rate is 51 ml / s.cm 2 . It can be seen from the comparison between the comparative example 1 and the example 2 that because of the addition of 12% of the additive component B, the 88A12B composite getter changes from not absorbing nitrogen to absorbing nitrogen. The specific component ratio, powder particle size and getter performance of the example 2 are shown in Table 1.

[0036] It can be found from Table 1 that when the metal oxide component of the main component A is 55% SiO2 20% Al2O3 20% CaO 5% C (x = 20 wt%; y = 20 wt%; Z = 10 wt%), if the additive component B metal compound Ti-Zr-V powder is not contained, i.e. 100% of the main component A 55% SiO2 20% Al2O3 20% CaO 5% C, it can be seen that the getter absorbs CO at a rate of 55 ml / s.cm 2 at room temperature, and the N2 absorption rate is 0.

[0037] When 12% of the additive component B, Ti-Zr-V getter, is added to 55% SiO2-20% Al2O3-20% CaO-5% C, a composite type [88%(55% SiO2-20% Al2O3-20% CaO-5% C)-12%(Ti-Zr-V)] getter (88%A-12%B) is formed. As can be seen, at room temperature, the rate of absorption of CO by the composite type 88%A-12%B getter is 54 ml / s.cm 2 and the rate of absorption of N2 is 51 ml / s.cm 2 The addition of the additive component B has caused the getter 55% SiO2-20% Al2O3-20% CaO-5% C, which does not absorb N2, to become the getter [88%(55% SiO2-20% Al2O3-20% CaO-5% C)-12%(Ti-Zr-V)] which absorbs N2.

[0038] The reason why the gettering performance of the 88%A-12%B composite type getter is increased in the 55% SiO2-20% Al2O3-20% CaO-5% C getter by the addition of 12% of the additive component B, the metal compound Ti-Zr-V getter, is that, as can be seen from Fig. 1, the additive component B contains Ti, Zr and V elements, and among these atoms, the 3d electron orbitals have unpaired electrons, which have a strong dissociation effect on impurity gases. It will break the C-O bond of the CO gas molecule and dissociate it into C and O atoms. In the same way, it will break the H-O bond of the H2O gas molecule and dissociate it into H and O atoms, and it will break the N-N bond of the N2 gas molecule and dissociate it into N atoms. This causes the CO gas molecule, the H2O gas molecule and the N2 gas molecule in the gas molecule to change into C, H and O atoms.

[0039] Because the atomic radius is much smaller than the gas molecule radius, the gas atoms rapidly diffuse toward the 88%A-12%B composite type getter formed by the composite type getter, thus achieving the effect of increasing the gettering rate.

[0040] Example 3, in which the main component A is 88% and the additive component B is 12%, is prepared by the following steps:

[0041] 1) 55% SiO2 powder, 25% Al2O3 powder, 20% CaO powder and 5% activated carbon powder, whose average particle size is 80 μm, are put into a ball mill of type KF-4L and ball milled. The alcohol added during ball milling is 6.5%, the balls used during ball milling are zirconia balls and the ball milling time is 5.9 hours. The powder obtained has an average particle size of 4.0 nm and component A is obtained.

[0042] 2) Preparation of the additive component B Zr-Ti-V metal compound getter: ① The Zr, Ti, V elements with purity of 99.9% were weighed according to the formula of Zr 43.49 Ti 2.54 V 53.97 wt%. ② The weighed raw materials were put into the copper crucible of the smelting furnace in the order of low melting point to high melting point, and then the smelting furnace was vacuumized to 3 x 10 -3 Pa, and then high-purity argon gas with purity of 99.9999% was introduced to wash the furnace, and then the vacuum was again vacuumized to 3 x 10 -3 Pa. ③ Then the alloy was smelted under the argon atmosphere with a pressure of 0.05 MPa. The CZL-300 type vacuum magnetic control tungsten electrode arc furnace was used for smelting. The power supply for arc smelting was turned on, the arc was started on the tungsten electrode, and then the arc was stabilized and smelting was performed on the titanium ingot. During smelting, the smelting current was about 100 A. The Zr 43.49 Ti 2.54 V 53.97 alloy was completely smelted and cast into an ingot. In order to ensure the uniformity of the Ti 2.54 V 53.97 alloy, the whole smelting process needed to be smelted for 4 times. After the Ti 2.54 V 53.97 alloy ingot was completely cooled after each smelting, it was turned over by a mechanical arm and smelted for 4 times again until it was uniform. ④ The smelted alloy was broken and ball milled under the protection of Ar atmosphere. The pressure of the protection atmosphere was 0.09 MPa, and the ball milling time was 3.5 h. The powder was ball milled to an average particle size of 32 μm to form the additive component B powder.

[0043] 3) The 99% main component A and the 1% additive component B were physically mixed to prepare a 99A1B composite powder getter. The specific surface area of the powder was 715 m 2 / g. The example 3 was activated at a vacuum degree of 5.0 x 10 -4 Pa and a temperature of 500°C for 20 min. The CO gas absorption performance at room temperature was 53 ml / s.cm 2 , and the nitrogen absorption rate was 5 ml / s.cm 2 . It can be seen from the comparison between the comparative example 1 and the example 3 that because of the addition of the additive component B with a content of 1%, the composite getter changes from not absorbing nitrogen to absorbing nitrogen. The specific component ratio, powder particle size, and gettering performance of the example 3 are shown in Table 1.

[0044] Example 4, in which the main component A has a content of 96% and the additive component B has a content of 4%, has the following preparation steps:

[0045] 1) 55% SiO2 powder, 25% Al2O3 powder, 20% CaO powder and 5% activated carbon powder were mixed. The average particle size of the four powders was 85 μm. The powders were put into a ball mill of KF-4L type. The alcohol was added to 7% during the ball milling. The zirconia balls were used during the ball milling. The ball milling time was 6.5 hours. The average particle size of the powder obtained was 4.2 nm. The component A was obtained.

[0046] 2) Preparation of the additive component B Zr-Ti-V metal compound getter: ① Zr, Ti and V elements with purity of 99.9% were weighed according to the mass ratio of Zr 43.49, Ti 2.54 and V 53.97 wt%. ② The weighed raw materials were put into the copper crucible of the smelting furnace in the order of low melting point to high melting point. Then the smelting furnace was vacuumized to 3.2 x 10 -3 Pa. Then high purity argon gas with purity of 99.9999% was introduced to wash the furnace. Then the smelting furnace was vacuumized to 3.5 x 10 -3 Pa again. ③ Then the alloy was smelted under the argon atmosphere with pressure of 0.05 MPa. The CZL-300 type vacuum magnetic control tungsten electrode arc furnace was used during the smelting. The power of the arc smelting was turned on. The arc was started on the tungsten electrode. Then the arc was stabilized and the alloy was smelted on the titanium ingot. The smelting current was about 110 A. The Zr 43.49 Ti 2.54 V 53.97 alloy was completely smelted and cast into ingot. In order to ensure the uniformity of the Ti 2.54 V 53.97 alloy, the alloy was smelted for 4 times. After the Ti 2.54 V 53.97 alloy ingot was cooled completely, the ingot was turned over by the mechanical arm and smelted for 4 times again until the alloy was uniform. ④ The smelted alloy was broken and ball milled under the argon atmosphere. The pressure of the argon atmosphere was 0.10 MPa. The ball milling time was 4 hours. The powder was ball milled to the average particle size of 31 μm. The additive component B powder was formed.

[0047] 3) 96% main component A and 4% additive component B were physically mixed to prepare the 99A1B composite powder getter. The specific surface area of the powder was 723 m 2 / g. The activation time of the example 4 was 20 minutes under the vacuum degree of 5.0 x 10 -4 Pa and the temperature of 500°C. The CO gas absorption rate of the example 4 was 51 ml / s.cm 2 at room temperature. The nitrogen absorption rate of the example 4 was 15 ml / s.cm 2 . It can be seen from the comparison between the comparative example 1 and the example 4 that the composite getter changes from not absorbing nitrogen to absorbing nitrogen because of the addition of 4% additive component B. The specific component ratio, the powder particle size and the gettering performance of the example 4 are shown in Table 1.

[0048] Example 5, wherein the host component A is 92% and the additive component B is 8%, and the preparation procedure is as follows:

[0049] 1) 55% SiO2 powder, 25% Al2O3 powder, 20% CaO powder and 5% activated carbon powder were mixed, and the average particle size of the four powders was 88 μm. The powders were put into a ball mill of KF-4L type, and alcohol was added during the ball milling at a rate of 7.7%. Zirconia balls were used during the ball milling, and the ball milling time was 6.5 hours. The average particle size of the obtained powder was 4.3 nm, and the component A was obtained.

[0050] 2) Preparation of the additive component B Zr-Ti-V metal compound getter material: ① Zr, Ti and V elements with a purity of 99.9% were weighed according to the formula of Zr 43.49Ti 2.54V 53.97wt%. ② The weighed raw materials were put into a copper crucible of a smelting furnace in the order of low melting point to high melting point, and then the smelting furnace was vacuumized to 3.5 x 10 -3 Pa. Then, high-purity argon gas with a purity of 99.9999% was introduced to wash the furnace, and then the smelting furnace was vacuumized to 3.7 x 10 -3 Pa again. ③ Then, the alloy was smelted under an argon atmosphere at a pressure of 0.05 MPa. A CZL-300 type vacuum magnetic control tungsten electrode arc furnace was used during the smelting. The power supply for the arc smelting was turned on, and the arc was started on the tungsten electrode, and then the arc was stabilized and the alloy was smelted on the titanium ingot. During the smelting, the smelting current was about 123 A. The Zr 43.49Ti 2.54V 53.97 alloy was completely smelted and cast into an ingot. In order to ensure the uniformity of the Ti 2.54V 53.97 alloy, the whole smelting process needed to be smelted for 4 times. After each smelting, the Ti 2.54V 53.97 alloy ingot was turned over by a mechanical arm and smelted for 4 times again until it was uniform. ④ The smelted alloy was broken and ball milled under an argon atmosphere. The pressure of the protective atmosphere was 0.11 MPa, and the ball milling time was 4.2 h. The powder was ball milled to an average particle size of 33 μm to form the additive component B powder.

[0051] 3) 96% of the host component A and 4% of the additive component B were physically mixed to prepare a 92A8B composite powder getter, and the specific surface area of the powder was 706 m 2 / g. The performance of the getter of Example 4 for absorbing CO gas at a vacuum degree of 5.0 x 10 -4 Pa and a temperature of 500°C for 20 min was 52 ml / s.cm 2 , and the gettering rate of nitrogen gas was 31 ml / s.cm 2Example 5 can be seen that because of the addition of component B 8%, the composite getter changes from not absorbing nitrogen to absorbing nitrogen. The specific component ratio, powder particle size, and getter performance of Example 5 are shown in Table 1.

[0052] Example 6, wherein the main component A is 84% and the additive component B is 16%, the preparation steps are as follows:

[0053] 1) 55% SiO2 powder, 25% Al2O3 powder, 20% CaO powder and 5% activated carbon powder. The average particle size of the four powders is 90 μm, which is put into a ball mill of KF-4L type for ball milling. The alcohol added during ball milling is 7.9%, the ball used during ball milling is zirconia ball, and the ball milling time is 6.5 hours. The average particle size of the obtained powder is 4.5 nm, and component A is obtained.

[0054] 2) Preparation of additive component B Zr-Ti-V metal compound getter material: ① The purity of Zr, Ti and V elements is 99.9%, and the ingredients are prepared according to the mass ratio of Zr 43.49Ti 2.54V 53.97wt%. ② The prepared raw materials are put into the copper crucible of the smelting furnace in the order of low melting point to high melting point, and then the smelting furnace is vacuumized to 3.5x10 -3 Pa, then high-purity argon gas with a purity of 99.9999% is introduced to wash the furnace, and then the vacuum is again vacuumized to 3.7x10 -3 Pa. ③ Then the alloy is melted under the argon atmosphere of 0.05 MPa. The CZL-300 type vacuum magnetic control tungsten electrode arc furnace is used for smelting. The power supply for open arc smelting is turned on, the arc is started on the tungsten electrode, and then the arc is stabilized and smelted on the titanium ingot. During smelting, the smelting current is about 131 A. The Zr 43.49Ti 2.54V 53.97 alloy is completely smelted and cast into an ingot. In order to ensure the uniformity of Ti 2.54V 53.97 alloy, the whole smelting process needs to be smelted for 4 times. After each smelting is completed, the Ti 2.54V 53.97 alloy ingot is turned over by a mechanical arm and smelted for 4 times until it is uniform. ④ The smelted alloy is broken and ball milled under the protection of Ar atmosphere, the pressure of the protection atmosphere is 0.13 MPa, and the ball milling time is 4.2 h. The powder is ball milled to an average particle size of 34 μm to form an additive component B powder.

[0055] 3) 84% main component A and 16% additive component B are physically mixed to prepare a 92A8B composite powder getter, and the specific surface area of the powder is 672 m 2 / g. Example 4 is carried out in a vacuum degree of 5.0x10 -4Pa, the CO gas absorption rate at 500°C for 20 min and at room temperature was 45 ml / s.cm 2 , the nitrogen gas absorption rate was 67 ml / s.cm 2 . As can be seen from Comparative Example 1 and Example 6, the composite getter changed from not absorbing nitrogen gas to absorbing nitrogen gas because of the addition of 16% of component B. The specific component ratio, powder particle size, and gas absorption performance of Example 6 are shown in Table 1.

[0056] Example 7, in which the main component A was 80% and the added component B was 20%, was prepared as follows:

[0057] 1) 55% SiO2 powder, 25% Al2O3 powder, 20% CaO powder, and 5% activated carbon powder were mixed, the average particle size of the four powders was 92 μm, and the powders were put into a KF-4L ball mill for ball milling, 8.3% alcohol was added during ball milling, zirconia balls were used during ball milling, the ball milling time was 8 hours, the average particle size of the obtained powder was 4.4 nm, and component A was obtained.

[0058] 2) Preparation of the added component B Zr-Ti-V metal compound getter material: ① Zr, Ti, and V elements with a purity of 99.9% were weighed according to the mass ratio of Zr 43.49:Ti 2.54:V 53.97 wt%; ② the weighed raw materials were sequentially put into a copper crucible of a smelting furnace according to the order of decreasing melting point, then the smelting furnace was vacuumized to 3.6 x 10 -3 Pa, then 99.9999% high-purity argon gas was introduced to wash the furnace, and then the smelting furnace was vacuumized to 4 x 10 -3 Pa; ③ the alloy was then smelted under an argon gas atmosphere at 0.05 MPa. A CZL-300 vacuum magnetic control tungsten electrode arc furnace was used for smelting. The power supply for arc smelting was turned on, an arc was struck on the tungsten electrode, and then the arc was stabilized and the alloy was smelted on the titanium ingot. During smelting, the smelting current was about 138 A. The Zr 43.49Ti 2.54V 53.97 alloy was completely smelted and cast into an ingot. In order to ensure the uniformity of the Ti 2.54V 53.97 alloy, the entire smelting process was smelted for 4 times, and after each smelting, the Ti 2.54V 53.97 alloy ingot was turned over by a mechanical arm and smelted for another 4 times until it was uniform; ④ the smelted alloy was broken and ball milled under an argon gas atmosphere, the pressure of the protective atmosphere was 0.14 MPa, and the ball milling time was 4.0 h. The powder was ball milled to an average particle size of 37 μm to form the added component B powder.

[0059] 3) 84% of the main component A and 16% of the additive component B are physically mixed to prepare a 92A8B composite powder getter, which has a specific surface of 658 m 2 / g. Example 4 was activated at 500°C for 20 min under a vacuum of 5.0 x 10 -4 Pa, and had a CO absorption rate of 43 ml / s.cm at room temperature. 2 The nitrogen absorption rate was 69 ml / s.cm. 2 Comparing Example 1 with Example 7, it can be seen that the composite getter changed from not absorbing nitrogen to absorbing nitrogen because of the addition of 16% of the component B. The specific composition, powder size, and absorption performance of Example 7 are shown in Table 1.

[0060] Example 8, in which the main component A is 76% and the additive component B is 24%, was prepared as follows:

[0061] 1) 55% of SiO2 powder, 25% of Al2O3 powder, 20% of CaO powder, and 5% of activated carbon powder were mixed. The average particle size of the four powders was 90 μm. The powders were put into a KF-4L ball mill, 8.1% of alcohol was added during the ball milling, zirconia balls were used during the ball milling, and the ball milling time was 7.8 hours. The average particle size of the obtained powder was 4.3 nm, and the component A was obtained.

[0062] 2) Preparation of the additive component B Zr-Ti-V metal compound getter: ① The Zr, Ti, and V elements with a purity of 99.9% were weighed according to the formula of Zr 43.49 Ti 2.54 V 53.97 wt%. ② The weighed raw materials were put into a copper crucible of a smelting furnace in order of decreasing melting point, and then the smelting furnace was vacuumed to 3.6 x 10 -3 Pa, and then 99.9999% high-purity argon was introduced to wash the furnace, and then the vacuum was again adjusted to 4 x 10 -3Pa. ③ Then melt the alloy under 0.05 MPa argon atmosphere. The vacuum magnetic control tungsten electrode arc furnace of CZL-300 type is used for melting. The arc power is turned on, and the arc is ignited on the tungsten electrode, then the arc is stabilized and the alloy is melted on the titanium ingot. The melting current is about 140 A. The Zr 43.49 Ti 2.54 V 53.97 alloy is completely melted and cast into ingot. In order to ensure the homogeneity of the Ti 2.54 V 53.97 alloy, the whole melting process needs to be melted for 4 times. After each melting, the Ti 2.54 V 53.97 alloy ingot is turned over by the mechanical arm and melted for 4 times until it is homogeneous. ④ The melted alloy is crushed and ball milled under the protection of Ar atmosphere. The pressure of the protection atmosphere is 0.14 MPa, and the ball milling time is 3.9 h. The powder is ball milled to an average particle size of 38 μm to form the additive component B powder.

[0063] 3) 76% of the main component A and 24% of the additive component B are physically mixed to prepare a 92A8B composite powder getter, and the specific surface area of the powder is 643 m 2 / g. In example 4, the activation is carried out at a vacuum degree of 5.0 x 10 -4 Pa and a temperature of 250°C for 20 min, and the CO gas absorption performance at room temperature is 40 ml / s.cm 2 , and the nitrogen absorption rate is 71 ml / s.cm 2 . It can be seen from the comparison between comparative example 1 and example 8 that the composite getter changes from not absorbing nitrogen to absorbing nitrogen because of the addition of 16% of the additive component B. The specific component ratio, powder particle size and absorption performance of example 7 are shown in table 1.

[0064] Example 9, in which the main component A is 88% and the additive component B is 12%, and the preparation steps are as follows:

[0065] 1) 55% of SiO2 powder, 25% of Al2O3 powder, 20% of CaO powder and 5% of activated carbon powder are mixed. The average particle size of the four powders is 90 μm, and the powders are put into a KF-4L type ball mill for ball milling. The alcohol added during ball milling is 8.1%, the balls used during ball milling are zirconia balls, and the ball milling time is 7.1 hours. The average particle size of the obtained powder is 4.5 nm, and the component A is obtained.

[0066] 2) Preparation of the additive component B Zr-Ti-V metal compound getter material: ① Zr, Ti and V elements with a purity of 99.9% are weighed according to the formula of Zr 43.49 Ti 2.54 V 53.97 wt%. ② The weighed raw materials are put into the copper crucible of the melting furnace in the order of low melting point to high melting point, and then the melting furnace is vacuumized to 3.6 x 10-3 Pa, then high purity argon gas of 99.9999% is introduced to wash the furnace, and then vacuum is extracted to 4x10 -3 Pa. 3) The alloy is then melted under an argon atmosphere of 0.05 MPa. The CZL-300 type vacuum magnetic control tungsten electrode arc furnace is used for melting. The power supply for arc melting is turned on, the arc is ignited on the tungsten electrode, and then the arc is stabilized and the alloy is melted on the titanium ingot. During the melting, the melting current is about 140 A. The Zr 43.49Ti 2.54V 53.97 alloy is completely melted and cast into an ingot. In order to ensure the uniformity of the Ti 2.54V 53.97 alloy, the entire melting process needs to be melted for 4 times. After each melting, the Ti 2.54V 53.97 alloy ingot is turned over by a mechanical arm and melted again for 4 times until it is uniform. 4) The melted alloy is crushed and ball milled under an argon atmosphere. The pressure of the protective atmosphere is 0.14 MPa, and the ball milling time is 4 h. The powder is ball milled to an average particle size of 35 μm to form the additive component B powder.

[0067] 3) 76% of the main component A and 24% of the additive component B are physically mixed to prepare a 92A8B composite powder getter, and the specific surface area of the powder is 643 m 2 / g. Example 4 is activated at a vacuum of 5.0x10 -4 Pa and a temperature of 250°C for 20 min, and the CO gas absorption performance at room temperature is 40 ml / s.cm 2 , and the nitrogen absorption rate is 71 ml / s.cm 2 . As can be seen from the comparison between Comparative Example 1 and Example 8, because of the addition of 16% of the additive component B, the composite getter changes from not absorbing nitrogen to absorbing nitrogen. The specific component ratio, powder particle size, and getter performance of Example 7 are shown in Table 1.

[0068] Example 10, in which the main component A is 88% and the additive component B is 12%, is prepared by the following steps:

[0069] 1) 55% of SiO2 powder, 25% of Al2O3 powder, 20% of CaO powder, and 5% of activated carbon powder are mixed. The average particle size of the four powders is 90 μm, and the powders are put into a KF-4L type ball mill. The alcohol added during ball milling is 8.1%, the balls used during ball milling are zirconia balls, and the ball milling time is 6.3 hours. The average particle size of the obtained powder is 5.8 nm, and component A is obtained.

[0070] 2) Preparation of component B Zr-Ti-V metal compound getter: ① The purity of 99.9% Zr, Ti, V elements, according to the mass ratio of Zr 43.49 Ti 2.54 V 53.97 wt% formula for ingredients. ② The prepared raw materials are placed in the copper crucible of the smelting furnace in the order of low to high melting point, and then the smelting furnace is vacuumed to 3.6 x 10 -3 Pa, then high-purity argon gas with a purity of 99.9999% is introduced to wash the furnace, and then vacuumed to 4 x 10 -3 Pa. ③ Then melt the alloy under the atmosphere of 0.05 MPa argon. The CZL-300 type vacuum magnetic tungsten electrode arc furnace is used for smelting. Turn on the power supply for arc smelting, first arc on the tungsten electrode, then stabilize the arc and smelt on the titanium ingot. During smelting, the smelting current is about 140 A. The Zr 43.49 Ti 2.54 V 53.97 alloy is completely smelted and cast into ingots. In order to ensure the uniformity of Ti 2.54 V 53.97 alloy, the whole smelting process needs to be smelted for 4 times, and after each smelting, the Ti 2.54 V 53.97 alloy ingot is turned over by a mechanical arm and smelted for 4 times until uniform. ④ The smelted alloy is broken and ball milled under the protection of Ar atmosphere, the pressure of the protection atmosphere is 0.14 MPa, and the ball milling time is 3.5 h. The powder is ball milled to an average particle size of 43 μm to form the component B powder.

[0071] 3) 76% of the main component A and 24% of the additive component B are physically mixed to prepare a 92A8B composite powder getter, and the specific surface area of the powder is 643 m 2 / g. The performance of the getter of example 4 is activated at a vacuum degree of 5.0 x 10 -4 Pa and a temperature of 250°C for 20 min, and the absorption rate of CO gas at room temperature is 40 ml / s.cm 2 , and the gettering rate of nitrogen gas is 71 ml / s.cm 2 . It can be seen from the comparison between comparative example 1 and example 8 that because of the addition of 16% of the additive component B, the composite getter changes from not absorbing nitrogen to absorbing nitrogen. The specific component ratio, powder particle size and gettering performance of example 7 are shown in Table 1.

[0072] Table 1

[0073] As can be seen from Table 1, the (SiO2) 1-x-y-z (Al2O3) x (CaO) y C zWhen x = 25wt%, y = 20wt%, Z = 5wt% in the getter, the composite getter 99A1B, 96A4B, 92A8B, 88A12B, 84A16B, 80A20B is formed by adding 0wt%, 1wt%, 4wt%, 8wt%, 12wt%, 16wt%, 24wt% of the additive component B to the getter (55% SiO2·25% Al2O3·20% CaO·5% C), respectively. These composite getters all have the ability to absorb N2 in addition to the ability to absorb CO at room temperature. The ability to absorb CO and N2 is 55ml / s.cm 2 , 0 (the getter is not a composite getter); 53ml / s.cm 2 , 5ml / s.cm 2 (99A1B composite getter); 51ml / s.cm 2 , 15ml / s.cm 2 (96A4B composite getter); 52ml / s.cm 2 , 31ml / s.cm 2 (92A8B composite getter); 54ml / s.cm 2 , 51ml / s.cm 2 (88A12B composite getter); 45ml / s.cm 2 , 67ml / s.cm 2 (84A16B composite getter); 43ml / s.cm 2 , 69ml / s.cm 2 (80A20B composite getter). It can be seen that with the addition of component B, the ability to absorb N2 gradually increases, and when the content of B is > 16%, the N2 absorption performance increases limitedly, but the CO performance has a downward trend, and when the content of component B is in the range of 12%-16%, the composite getter aAbB has the best gettering performance.

[0074] At the same time, it can be seen from Table 1 that, under the same content of component B, the smaller the powder particle size and the larger the specific surface area, the stronger the gettering ability. For example, by comparing Example 2 with Examples 9 and 10, it can be seen that, with the same composite getter 88A12B, by comparing the average powder particle size of component A and component B of Comparative Example 2 with Examples 9 and 10, it can be seen that, with the decrease of the powder particle size of these composite getters, the ability to absorb CO and N2 at room temperature increases. With the decrease of the powder particle size, the ability to absorb CO and N2 increases from 47ml / s.cm 2 , 43ml / s.cm 2 (A particle size and B particle size are 5.8nm and 43μm, respectively) to 54ml / s.cm 2 , 51ml / s.cm2 (A particle size and B particle size are 3.1 nm and 30 μm respectively), so when A group element 3-4 nm, B group element is in 30-35 um, the composite type getter aAbB has the best gettering performance.

[0075] In summary, in the main group element A (SiO2) 1-x-y-z (Al2O3) x (CaO) y C z On the basis, add the additive group element B, and because the main group element A and the additive group element B powder particle size is refined, the coupling effect of the two getter combination is obvious, so that the composite type getter has the ability to absorb N2 on the basis of absorbing CO.

[0076] The above-described above examples are only used to illustrate the technical solutions of the present application, but not to limit it; although the present application has been described in detail with reference to the foregoing examples, those skilled in the art should understand that: it can still modify the technical solutions recorded in the foregoing examples, or make equivalent replacement for part of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the present application.

Claims

1. A composite getter material having a high efficiency of absorption of nitrogen, characterized in that, The composite getter material comprises a main component A and an additive component B, and the main component A and the additive component B form an aAbB composite getter, wherein a+b=100%, 50wt%≤a<100wt%, and 0wt%<b<50wt%; The main component A comprises the following components: (SiO2) 1-x-y-z (Al2O3) x (CaO) y C z 20wt%≤x≤70wt%, 10wt%≤y≤60wt%, and 0wt%≤z≤40wt%; The additive component B is a metal compound Zr-Ti-V getter material.

2. The composite getter material with high efficiency of nitrogen absorption according to claim 1, characterized in that, The main component A is a powder with a particle size of 3-5 nm.

3. The composite getter material with high efficiency of nitrogen absorption according to claim 1, characterized in that, The additive component B is a powder with a particle size of 8-50 microns.

4. The composite getter material with high efficiency of nitrogen absorption according to claim 1, characterized in that, In the aAbB composite getter, 60wt%≤a≤95wt%, and 1wt%≤b≤40wt%.

5. The composite getter material with high efficiency of nitrogen absorption according to claim 1, characterized in that, The preparation method of the main component A comprises the following steps: SiO2, Al2O3, CaO, and activated carbon C powder are put into a ball mill according to the component ratio, 5-15wt% alcohol is added during the ball milling, zirconia balls are used for ball milling, the diameter of the balls is 5-300 mm, the ball-to-material ratio is 1-3, and the ball milling time is 5-10 hours, so that the main component A mixed powder with a particle size of 3-5 nm is obtained.

6. The composite getter material with high efficiency of nitrogen absorption according to claim 1, characterized in that, The preparation method of the additive component B comprises the following steps: Zr, Ti, and V elements with a purity of 99.9% are proportioned according to the mass ratio; The prepared raw materials are put into the copper crucible of the smelting furnace in order of low to high melting point, and then the smelting furnace is vacuumized to 1-5*10 -3 Pa, and then 99.9999% high-purity argon is introduced to wash the furnace, and then the smelting furnace is vacuumized to 1-5*10 -3 Pa again. Then, the alloy is melted under an argon atmosphere with a pressure of 0.05 MPa, a vacuum magnetron tungsten electrode arc furnace is used for melting, the power supply for arc melting is turned on, an arc is first generated on the tungsten electrode, then the arc is stabilized and the alloy is melted on the titanium ingot, the melting current is about 80-220 A during the melting, so that the alloy is completely melted and poured into an ingot, the whole melting process needs to be repeated for 4 times, after each melting, the Ti V alloy ingot is fully cooled, then the Ti V alloy ingot is turned over by a mechanical arm and melted for 4 times again until it is uniform; The melted alloy is crushed and ball milled under a protective atmosphere, the pressure of the protective atmosphere is 0.04-0.2 MPa, and the ball milling time is 2-10 hours, so that the additive component B powder with a particle size of 270 mesh-1800 mesh and 8-50 microns is obtained.

7. A method for producing a composite getter material having a high efficiency of absorption of nitrogen, characterized in that, The preparation method of the main component A comprises the following steps: SiO2, Al2O3, CaO, and activated carbon C powder are put into a ball mill according to the component ratio, 5-15wt% alcohol is added during the ball milling, zirconia balls are used for ball milling, the diameter of the balls is 5-300 mm, the ball-to-material ratio is 1-3, and the ball milling time is 5-10 hours, so that the main component A mixed powder with a particle size of 3-5 nm is obtained. Zr, Ti, and V elements with a purity of 99.9% are proportioned according to the mass ratio; The prepared raw materials are put into the copper crucible of the smelting furnace in order of low to high melting point, and then the smelting furnace is vacuumized to 1-5*10 -3 Pa, and then 99.9999% high-purity argon is introduced to wash the furnace, and then the smelting furnace is vacuumized to 1-5*10 -3 Pa again. Then, the alloy is melted under an argon atmosphere with a pressure of 0.05 MPa, a vacuum magnetron tungsten electrode arc furnace is used for melting, the power supply for arc melting is turned on, an arc is first generated on the tungsten electrode, then the arc is stabilized and the alloy is melted on the titanium ingot, the melting current is about 80-220 A during the melting, so that the alloy is completely melted and poured into an ingot, the whole melting process needs to be repeated for 4 times, after each melting, the Ti V alloy ingot is fully cooled, then the Ti V alloy ingot is turned over by a mechanical arm and melted for 4 times again until it is uniform; The melted alloy is crushed and ball milled under a protective atmosphere for 2-10 h to obtain the additive component B, wherein the pressure of the protective atmosphere is 0.04-0.2 MPa, and the powder is ball milled to 270-1800 mesh, 8-50 microns; The main component A and the additive component B are physically mixed to form aAbB component.

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