阅读说明：本技术 一种纳米镍保护层吸气材料的制备方法 (Preparation method of nano nickel protective layer getter material ) 是由 鲁涛 于 2019-10-16 设计创作，主要内容包括：本发明公布了一种纳米镍保护层吸气材料的制备方法,制备方法是按以下步骤进行的：将吸气合金中的原料按一定比例进行配制,通过熔炼的方法制备成合金,然后对合金在保护气氛下进行破碎和球磨,获得325目~80目的吸气合金粉末；将上述吸气合金粉末放在钢性模具中进行压制形成压坯；将压坯用镍箔将包覆,确保压坯的每个面暴露在镍箔环境中；对用镍箔将包覆的压坯在真空度为3~5×10<Sup>-3</Sup> Pa进行真空烧结,等真空烧结炉冷至室温时,出炉即可。本发明防止在大气环境下吸气剂表面氧化等问题,又能在实际的工装使用环境下,维持真空器件的高真空度、长寿命、高可靠性,如对电子管、激光管、电光源等的真空器件中的残余气体吸收具有高可靠性。(The invention discloses a preparation method of a nano nickel protective layer getter material, which is carried out according to the following steps: in the getter alloyThe raw materials are prepared according to a certain proportion, the alloy is prepared by a smelting method, and then the alloy is crushed and ball-milled under a protective atmosphere to obtain 325-80 mesh air suction alloy powder; putting the getter alloy powder in a rigid die to be pressed to form a pressed compact; coating the green compact with nickel foil to ensure that each side of the green compact is exposed to the nickel foil environment; subjecting a green compact coated with a nickel foil to a vacuum of 3 to 5X 10 ‑3 And (4) carrying out vacuum sintering on Pa, and discharging the product when the vacuum sintering furnace is cooled to room temperature. The invention can prevent the problems of surface oxidation of the getter in the atmospheric environment and the like, and can maintain the high vacuum degree, the long service life and the high reliability of the vacuum device in the actual tool use environment, such as the high reliability of residual gas absorption in vacuum devices such as electron tubes, laser tubes, electric light sources and the like.)

1. A preparation method of a nano nickel protective layer getter material is characterized by comprising the following steps:

1) preparing raw materials in the air suction alloy according to a certain proportion, preparing the air suction alloy into an alloy by a smelting method, and then crushing and ball-milling the alloy in a protective atmosphere to obtain 325-80 mesh air suction alloy powder;

2) putting the getter alloy powder in a rigid die to be pressed to form a pressed compact;

3) coating the green compact with nickel foil to ensure that each side of the green compact is exposed to the nickel foil environment;

4) subjecting a green compact coated with a nickel foil to a vacuum of 3 to 5X 10^-3And (4) carrying out vacuum sintering on Pa, and discharging the product when the vacuum sintering furnace is cooled to room temperature.

2. The method for preparing a nano-nickel protective layer getter material according to claim 1, wherein: the getter alloys are of the type comprising:

a) Zr-Al alloy, Zr-Al-RE alloy, Zr-Al-TE-RE alloy, wherein TE comprises transition group elements of Ti, Fe, Co, Ni, Mn, Pd, Ru, Pt, V, Cr, Nb, Mo, Tc, Rh, Hf, Ta, W, Re, Os and Ir;

b) Zr-C alloy, Zr-C-RE alloy, Zr-C-TE-RE alloy, wherein TE comprises transition group elements of Ti, Fe, Co, Ni, Mn, Pd, Ru, Pt, V, Cr, Nb, Mo, Tc, Rh, Hf, Ta, W, Re, Os and Ir;

c) Zr-V-Fe alloy, Zr-V-Fe-RE alloy, Zr-V-Fe-TE alloy, Zr-V-Fe-RE-TE alloy, wherein TE comprises transition elements of Ti, Co, Ni, Mn, Pd, Ru, Pt, Cr, Nb, Mo, Tc, Rh, Hf, Ta, W, Re, Os and Ir;

d) Zr-Co alloy, Zr-Co-RE alloy, Zr-Co-TE alloy, Zr-Co-RE-TE alloy, wherein TE comprises transition group elements of Ti, Fe, Ni, Mn, Pd, Ru, Pt, V, Cr, Nb, Mo, Tc, Rh, Hf, Ta, W, Re, Os and Ir;

e) Ti-Mo alloy, Ti-Mo-RE alloy, Ti-Mo-TE alloy, Ti-Mo-RE-TE alloy, wherein TE comprises transition group elements of Zr, Fe, Co, Ni, Mn, Pd, Ru, Pt, V, Cr, Nb, Tc, Rh, Hf, Ta, W, Re, Os and Ir;

f) Ti-Zr-V alloy, Ti-Zr-V-RE alloy, Ti-Zr-V-TE-RE alloy, wherein TE comprises transition group elements of Fe, Co, Ni, Mn, Pd, Ru, Pt, Cr, Nb, Mo, Tc, Rh, Hf, Ta, W, Re, Os and Ir;

g) Zr-Co-Re (rhenium) alloy, Zr-Co-Re-RE-TE alloy, wherein TE comprises transition elements of Ti, Fe, Co, Ni, Mn, Pd, Ru, Pt, V, Cr, Nb, Mo, Tc, Rh, Hf, Ta, W, Os and Ir.

3. The method for preparing a getter material with a nano-nickel protective layer according to claim 2, wherein: and RE is rare earth elements Y, Sc, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu.

4. The method for preparing a nano-nickel protective layer getter material according to claim 1, wherein: the forming pressure of the getter alloy powder in the rigid die is 1-200 Mpa, and the pressure is maintained for 1-30 s.

5. The method for preparing a nano-nickel protective layer getter material according to claim 1, wherein: the relative density of the pressed compact is 30-60%.

6. The method for preparing a nano-nickel protective layer getter material according to claim 1, wherein: the thickness of the nickel is 0.005-0.5 mm.

7. The method for preparing a nano-nickel protective layer getter material according to claim 1, wherein: the sintering process of the pressed compact is to keep the temperature at 1000-1300 ℃ for 0.2-2 h.

8. The method for preparing a nano-nickel protective layer getter material according to claim 1, wherein: the nickel foil volatilizes nickel vapor during high-temperature sintering, and the nickel vapor is deposited on a pressed compact to form a nano nickel thin layer.

Technical Field

The invention relates to the field of packaging of vacuum devices, in particular to a preparation method of a nano nickel protective layer getter material.

Background

At present, the bulk getter materials are prepared mainly by powder metallurgy. Its working process means that after activation treatment, an active surface is obtained and can be reused. The getter material does not change its morphology during activation. The getter material undergoes a specific activation process followed by decomposition of the purification layer on the surface, exposing the active surface in the metallic state, capable of undergoing a physicochemical reaction with the active gas molecules to getter.

In the case of bulk getter materials, it adsorbs the active gases when the active surface is exposed after the vacuum activation process. Surface adsorption, surface and interface migration, and bulk diffusion are the main mechanisms of the gas adsorption behavior of its bulk getter material. Bulk getter materials are porous materials sintered by means of powder metallurgy. The porous sintered getter has the advantages of large porosity, large specific surface area and the like. However, these features of large specific surface area and large porosity are prone to adsorption and oxidation when in contact with the atmosphere, and are prone to dusting during activation processes requiring vacuum induction or vacuum baking.

Disclosure of Invention

The invention aims to provide a preparation method of a nano nickel protective layer getter material which is difficult to shed powder and oxidize.

The purpose of the invention is realized as follows: the preparation method of the nano nickel protective layer getter material is carried out according to the following steps:

1) preparing raw materials in the air suction alloy according to a certain proportion, preparing the air suction alloy into an alloy by a smelting method, and then crushing and ball-milling the alloy in a protective atmosphere to obtain 325-80 mesh air suction alloy powder;

2) putting the getter alloy powder in a rigid die to be pressed to form a pressed compact;

3) coating the green compact with nickel foil to ensure that each side of the green compact is exposed to the nickel foil environment;

4) subjecting a green compact coated with a nickel foil to a vacuum of 3 to 5X 10^-3And (4) carrying out vacuum sintering on Pa, and discharging the product when the vacuum sintering furnace is cooled to room temperature.

Compared with the prior art, the invention has the advantages that: compared with the getter alloy which is not coated with nickel layer, the getter alloy has obvious advantages, such as obviously increased getter efficiency. The nanometer nickel layer can be as block getter protective layer, prevents the problem such as getter surface oxidation under atmospheric environment, again can be under the frock service environment of reality, at its activation in-process, because nanometer nickel layer cladding effect has prevented the powder phenomenon that falls among the activation process, and colleague because the good heat conduction of nanometer nickel layer is special, can make its activation in-process heat conduct gradually and be heated evenly for the activation becomes easy. And the nano nickel thin layer does not influence the air suction performance of the block material. The getter material coated with the nano nickel layer can maintain high vacuum degree, long service life and high reliability of vacuum devices after vacuum activation, and has high reliability on residual gas absorption in vacuum devices such as electron tubes, laser tubes, electric light sources and the like.

In a preferred embodiment of the present invention, the getter alloy includes:

a) Zr-Al alloy, Zr-Al-RE alloy, Zr-Al-TE-RE alloy, wherein TE comprises transition group elements of Ti, Fe, Co, Ni, Mn, Pd, Ru, Pt, V, Cr, Nb, Mo, Tc, Rh, Hf, Ta, W, Re, Os and Ir;

b) Zr-C alloy, Zr-C-RE alloy, Zr-C-TE-RE alloy, wherein TE comprises transition group elements of Ti, Fe, Co, Ni, Mn, Pd, Ru, Pt, V, Cr, Nb, Mo, Tc, Rh, Hf, Ta, W, Re, Os and Ir;

c) Zr-V-Fe alloy, Zr-V-Fe-RE alloy, Zr-V-Fe-TE alloy, Zr-V-Fe-RE-TE alloy, wherein TE comprises transition elements of Ti, Co, Ni, Mn, Pd, Ru, Pt, Cr, Nb, Mo, Tc, Rh, Hf, Ta, W, Re, Os and Ir;

d) Zr-Co alloy, Zr-Co-RE alloy, Zr-Co-TE alloy, Zr-Co-RE-TE alloy, wherein TE comprises transition group elements of Ti, Fe, Ni, Mn, Pd, Ru, Pt, V, Cr, Nb, Mo, Tc, Rh, Hf, Ta, W, Re, Os and Ir;

e) Ti-Mo alloy, Ti-Mo-RE alloy, Ti-Mo-TE alloy, Ti-Mo-RE-TE alloy, wherein TE comprises transition group elements of Zr, Fe, Co, Ni, Mn, Pd, Ru, Pt, V, Cr, Nb, Tc, Rh, Hf, Ta, W, Re, Os and Ir;

f) Ti-Zr-V alloy, Ti-Zr-V-RE alloy, Ti-Zr-V-TE-RE alloy, wherein TE comprises transition group elements of Fe, Co, Ni, Mn, Pd, Ru, Pt, Cr, Nb, Mo, Tc, Rh, Hf, Ta, W, Re, Os and Ir;

g) Zr-Co-Re (rhenium) alloy, Zr-Co-Re-RE-TE alloy, wherein TE comprises transition elements of Ti, Fe, Co, Ni, Mn, Pd, Ru, Pt, V, Cr, Nb, Mo, Tc, Rh, Hf, Ta, W, Os and Ir.

In a further preferred embodiment of the present invention, RE is a rare earth element Y, Sc, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu.

In a further preferred embodiment of the present invention, the getter alloy powder is molded in a rigid mold under a pressure of 1 to 200 MPa for 1 to 30 seconds,

in a more preferred embodiment of the present invention, the green compact has a relative density of 30 to 60%.

In a further preferred embodiment of the present invention, the nickel is thin and has a thickness of 0.005 to 0.5 mm. .

As a further preferable scheme of the invention, the sintering process of the pressed compact is to keep the temperature at 1000-1300 ℃ for 0.2-2 h.

In a further preferred embodiment of the present invention, the nickel foil volatilizes nickel vapor during high-temperature sintering, and the nickel vapor is deposited on the green compact to form a nano-nickel thin layer.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The preparation method of the nano nickel protective layer getter material is carried out according to the following steps:

1) preparing raw materials in the air suction alloy according to a certain proportion, preparing the air suction alloy into an alloy by a smelting method, and then crushing and ball-milling the alloy in a protective atmosphere to obtain 325-80 mesh air suction alloy powder;

2) putting the getter alloy powder in a rigid die to be pressed to form a pressed compact;

3) coating the green compact with nickel foil to ensure that each side of the green compact is exposed to the nickel foil environment;

4) and (3) carrying out vacuum sintering on the coated green compact by using the nickel foil at the vacuum degree of 3-5 multiplied by 10 < -3 > Pa, and discharging the green compact when the vacuum sintering furnace is cooled to room temperature.

The types of getter alloys include:

a) Zr-Al alloy, Zr-Al-RE alloy, Zr-Al-TE-RE alloy, wherein TE comprises transition group elements of Ti, Fe, Co, Ni, Mn, Pd, Ru, Pt, V, Cr, Nb, Mo, Tc, Rh, Hf, Ta, W, Re, Os and Ir;

b) Zr-C alloy, Zr-C-RE alloy, Zr-C-TE-RE alloy, wherein TE comprises transition group elements of Ti, Fe, Co, Ni, Mn, Pd, Ru, Pt, V, Cr, Nb, Mo, Tc, Rh, Hf, Ta, W, Re, Os and Ir;

c) Zr-V-Fe alloy, Zr-V-Fe-RE alloy, Zr-V-Fe-TE alloy, Zr-V-Fe-RE-TE alloy, wherein TE comprises transition elements of Ti, Co, Ni, Mn, Pd, Ru, Pt, Cr, Nb, Mo, Tc, Rh, Hf, Ta, W, Re, Os and Ir;

d) Zr-Co alloy, Zr-Co-RE alloy, Zr-Co-TE alloy, Zr-Co-RE-TE alloy, wherein TE comprises transition group elements of Ti, Fe, Ni, Mn, Pd, Ru, Pt, V, Cr, Nb, Mo, Tc, Rh, Hf, Ta, W, Re, Os and Ir;

e) Ti-Mo alloy, Ti-Mo-RE alloy, Ti-Mo-TE alloy, Ti-Mo-RE-TE alloy, wherein TE comprises transition group elements of Zr, Fe, Co, Ni, Mn, Pd, Ru, Pt, V, Cr, Nb, Tc, Rh, Hf, Ta, W, Re, Os and Ir;

f) Ti-Zr-V alloy, Ti-Zr-V-RE alloy, Ti-Zr-V-TE-RE alloy, wherein TE comprises transition group elements of Fe, Co, Ni, Mn, Pd, Ru, Pt, Cr, Nb, Mo, Tc, Rh, Hf, Ta, W, Re, Os and Ir;

g) Zr-Co-Re (rhenium) alloy, Zr-Co-Re-RE-TE alloy, wherein TE comprises transition elements of Ti, Fe, Co, Ni, Mn, Pd, Ru, Pt, V, Cr, Nb, Mo, Tc, Rh, Hf, Ta, W, Os and Ir.

The RE is rare earth elements Y, Sc, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu.

The forming pressure of the getter alloy powder in a rigid mold is 1-200 Mpa, and the pressure is maintained for 1-30 s,

the relative density of the green compact is 30-60%.

The nickel is thin and has a thickness of 0.005 to 0.5 mm. .

The sintering process of the pressed compact is to keep the temperature at 1000-1300 ℃ for 0.2-2 h.

The nickel foil volatilizes nickel vapor during high-temperature sintering, and the nickel vapor is deposited on a pressed compact to form a nano nickel thin layer.