CN114749672B - Preparation method and application of high-purity ZrAl1 powder - Google Patents

Preparation method and application of high-purity ZrAl1 powder Download PDF

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CN114749672B
CN114749672B CN202210328301.1A CN202210328301A CN114749672B CN 114749672 B CN114749672 B CN 114749672B CN 202210328301 A CN202210328301 A CN 202210328301A CN 114749672 B CN114749672 B CN 114749672B
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zral1
powder
purity
furnace
alloy ingot
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CN114749672A (en
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熊玉华
张庆猛
杜昊瑾
郭德宇
杨志民
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GRIMN Engineering Technology Research Institute Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/023—Hydrogen absorption
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C16/00—Alloys based on zirconium
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E30/00—Energy generation of nuclear origin
    • Y02E30/30—Nuclear fission reactors

Abstract

A method for preparing high-purity ZrAl1 powder and application thereof, wherein the method comprises the following steps: preparing ZrAl1 alloy ingot by adopting a suspension smelting method, loading the ZrAl1 alloy ingot into a hydrogenation dehydrogenation furnace, vacuumizing, heating the alloy ingot, then charging hydrogen, charging hydrogen again when the pressure drop of hydrogen in the furnace is 0.01-0.04 MPa, repeating charging hydrogen for 5-8 times, starting cooling after the pressure drop of hydrogen in the furnace is 0.01-0.04 MPa, and charging high-purity Ar into the furnace after the temperature is reduced to 100-200 ℃; taking out the ZrAl1 alloy ingot, mechanically crushing and screening; and carrying out dehydrogenation treatment on the ZrAl1 alloy powder for 1-3 times, and vacuumizing and packaging for standby. The ZrAl1 alloy powder prepared by the method is used as a reducing agent to prepare a Na source, and the Na source is applied to the photocathode of the ultra-second generation low-light-level night vision device, so that the result shows that the evaporation characteristic of the Na source meets the preparation requirement of the photocathode of the ultra-second generation low-light-level image intensifier.

Description

Preparation method and application of high-purity ZrAl1 powder
Technical Field
The invention belongs to the field of sodium source release agents and release devices for ultra-second-generation low-light night vision devices, and particularly relates to a preparation method and application of high-purity ZrAl1 powder.
Background
The low-light night vision device is a night vision device developed in the 60 th century. The night observation instrument is a night observation instrument which can enhance the glimmer light reflected by the target through the image enhancer and can enable human eyes to see the target image. The low-light night vision device does not need an active light source and is a passive imaging system, so that the defect that the active infrared night vision device is easy to expose is overcome, and the low-light night vision device is more suitable for army night combat.
The low-light level image intensifier is the core of low-light level night vision device, and the image intensifier mainly produced in China at present is a super-second-generation image intensifier, and the structure of the low-light level image intensifier comprises a cathode glass window, a photocathode, a microchannel plate, a fluorescent screen, an optical fiber output window and the like. The photoelectric cathode can generate an external photoelectric effect, plays a role of weak light imaging, and when a weak light image is incident on the super-second-generation image intensifier, incident light firstly penetrates through a cathode glass window, then reaches the photoelectric cathode and excites photoelectrons. The photocathode is the core of the image intensifier. The photoelectrode of the super-second-generation image intensifier is an Sb-Na-K-Cs multi-alkali photoelectrode, which is formed by depositing a layer of Na with a single atomic cesium layer on the surface on a substrate under the high vacuum condition 2 A KSb P-type semiconductor, which belongs to a positron affinity photocathode. At present, the standard process for manufacturing the multi-alkali photocathode still adopts the thermal evaporation coating process given by A.H. Sommer: evaporating antimony and potassium to form K 3 Sb film layer-sodium steaming to form Na >2 K <1 Sb film layer, alternately steaming antimony, potassium and sodium to form Na 2 KSb structural film layer-alternate cesium and antimony evaporation to form Na 2 KSb (Cs) cathode. In the process of preparing the photocathode, various alkali sources such as a K source, a Na source and a Cs source are required to be used, and corresponding alkali metal vapor is formed on the surface of the photocathode to form Na 2 The quality of the alkali source determines the cathode quality, KSb (Cs).
The alkaline source for photocathode is generally composed of mixed powder of alkali metal salt and reducing agent, niCr electrothermal alloy shell, terminal electrode and alkali metal vapor escape outlet on the shell. Under vacuum condition, the shell is electrified and heated, and then the mixed powder of alkali metal salt and reducing agent is heated, the alkali metal in the alkali metal salt is reduced by the reducing agent to form vapor, and the alkali metal vapor escapes from the vapor escape outlet and is deposited on the photocathode. Among them, na metal salts used in Na source are sodium chromate, sodium molybdate, etc., and if conventional zirconium aluminum 16 (ZrAl 16, zr-16wt.% Al) is used as a reducing agent, there is a problem that the reaction rate is slow. Therefore, a reducing agent capable of replacing zirconium-aluminum 16 powder and improving the reaction rate needs to be found and used for preparing a sodium source of a photocathode of a low-light-level image intensifier.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a preparation method and application of high-purity ZrAl1 (Zr-1 wt.% Al) reducer powder in a sodium source releasing agent for a super-second-generation low-light night vision device.
The invention is realized by the following technical scheme.
The preparation method of the high-purity ZrAl1 powder is characterized by comprising the following steps of:
(1) Preparing a ZrAl1 alloy ingot by adopting a suspension smelting method;
(2) The ZrAl1 alloy ingot is put into a hydrogenation dehydrogenation furnace, and is vacuumized until the air pressure in the hydrogenation dehydrogenation furnace chamber is less than 1 multiplied by 10 - 4 Heating an alloy ingot to 300-500 ℃ and preserving heat for 1-2 h under Pa, then filling hydrogen with the pressure of 0.2-0.5 MPa, filling hydrogen again under the pressure drop of 0.01-0.04 MPa in a furnace, repeatedly filling hydrogen for 5-8 times, starting cooling after the pressure drop of 0.01-0.04 MPa in the furnace, and filling high-purity Ar with the pressure of more than 0.1MPa and less than 0.5MPa in the furnace after cooling to 100-200 ℃;
(3) Taking out the ZrAl1 alloy ingot obtained in the step (2), and mechanically crushing and screening;
(4) Carrying out dehydrogenation treatment on the ZrAl1 alloy powder obtained in the step (3) for 1-3 times;
(5) And (3) vacuumizing and packaging the ZrAl1 powder obtained in the step (4) for standby.
Further, in the step (1), the smelting cavity is vacuumized to 10 ℃ before smelting -2 Pa magnitude, then filling high-purity Ar, and repeatedly flushing for 2-3 times; by suspension smeltingThe number of suspension smelting times for preparing ZrAl1 alloy ingot is 3-4 times.
And (2) removing oxide on the surface of the ZrAl1 alloy ingot before loading the ZrAl1 alloy ingot into a hydrogenation dehydrogenation furnace, and carrying out opening treatment.
Further, in the step (2), the hydrogenation and dehydrogenation furnace is used for high-purity H before vacuumizing 2 Flushing for 2-4 times.
Further, high-purity Ar gas is filled into a screen mesh adopted in the step (3) for protection, then ZrAl1 alloy powder with the required granularity is screened out by a screen shaker, and the screen shaking time is 1-3 min.
Further, the mesh number (or pore size) of the screen may be selected according to a desired particle size range, such as-80 to +300 mesh, -150 to +250 mesh, or-300 mesh.
Further, the step (4) of dehydrogenation treatment is to lay the obtained ZrAl1 alloy powder in a molybdenum box, and put the molybdenum box into a hydrogenation and dehydrogenation furnace, when the air pressure in the hydrogenation and dehydrogenation furnace chamber is less than 1 multiplied by 10 -4 In Pa, the powder is heated, the dehydrogenation treatment temperature is 500-700 ℃, the heat preservation time is 0.5-1.5 hours, and the powder needs to be screened again after each dehydrogenation treatment.
The high-purity ZrAl1 powder prepared by the method is characterized in that the high-purity ZrAl1 powder is used as a reducing agent of a sodium source and is used for absorbing active impurity gas.
Further, the active impurity gas is one or more mixed gases of hydrogen, oxygen, nitrogen, water vapor, carbon monoxide and carbon dioxide.
Further description of the invention: the Na source, either Na metal salt or zral1 reducing agent, is used in powder form for uniformity and sufficient reaction. The content of low-melting impurities in the ZrAl1 reducer powder significantly affects the purity of released Na vapor, the content of oxides on the surface of the powder affects the temperature and the rate of the reduction reaction, and the particle size of the reducer powder affects the reaction rate of Na metal salt and the reducer powder. That is, the purity and particle size of the ZrAl1 reductant powder affects the control of the Na vapor release reaction andthe purity of Na vapor can further affect the fabrication process and performance of the photocathode. To ensure purity of Na vapor, it is required to use high purity zral1 reducing agent powder. As can be seen from the phase diagram, the main phase in ZrAl1 is an alpha-Zr solid solution, and a very small amount of Zr is contained 3 Al is difficult to obtain granular alloy powder by directly adopting a conventional mechanical pulverizing method because the ductility of the alpha-Zr solid solution is good. The invention provides a preparation method of high-purity ZrAl1 powder, which relates to suspension smelting preparation of a high-purity ZrAl1 alloy ingot and hydrogenation and dehydrogenation method preparation of the ZrAl1 powder, and the high-purity ZrAl1 alloy powder with required granularity can be obtained by the process steps of firstly hydrogenating, crushing, screening, dehydrogenating and the like the ZrAl1 alloy ingot and the adapted process conditions, wherein the granularity of the prepared-80- +300 mesh powder: d10 is 71 to 74 μm, D50 is 143 to 145 μm, and D90 is 261 to 266 μm. Because of the problems of impurity introduction into a Cu crucible in suspension smelting, hydrogen residue in hydrogenation and dehydrogenation treatment, easy oxidation of the surface of active ZrAl1 powder and the like (the influence of Cu crucible, H and O impurities exists), the purity of the high-purity ZrAl1 alloy powder prepared by the method of the invention>99.5% (wt.%) (zral1 alloy powder purity was defined as the sum of ((zr+al) element mass/(zr+al+cu+h+o) element mass).
The ZrAl1 alloy powder prepared by the method has high purity, is used as a reducing agent to prepare a Na source, and is applied to the photocathode of the ultra-second-generation low-light night vision device, and the result shows that the evaporation characteristic of the Na source meets the preparation requirement of the photocathode of the ultra-second-generation low-light image intensifier.
Drawings
FIG. 1 is an XRD pattern of ZrAl1 alloy powder.
FIG. 2 is a graph showing the results of the hydrogen absorption performance test of ZrAl1 alloy powder.
FIG. 3 is a morphology of a-300 mesh ZrAl1 alloy powder prepared by a hydrodeoxygenation process.
Detailed Description
The invention will be described in detail below with reference to the drawings and the detailed description.
According to the research, under the condition that other technological parameters are the same, when the Na source adopts ZrAl1 powder as a reducing agent, the reaction rate is faster than that of ZrAl16 powder, the average evaporation rate is increased by 21.1%, the maximum instantaneous evaporation rate is increased by 31.6%, and the evaporation rate is increased by 142.9%. In addition, the air suction performance test is carried out by adopting a constant pressure method, and the ZrAl1 powder is found to have better hydrogen suction performance under the activation condition of heat preservation at 350 ℃ for 30 minutes, wherein the initial hydrogen suction rate is more than 850 ml/s.g, and the accumulated hydrogen suction amount in 120 minutes is more than 1150 Pa.ml/g.
Principle of constant pressure method: the room temperature hydrogen absorption performance of the getter is tested by adopting a constant pressure method, and the constant pressure method is a common method for measuring the air absorption performance of the getter material. The measurement principle is based on the difference in gas pressure at the two ends of a capillary (or orifice) through which a molecular gas flow passes, typically by a constant getter material chamber pressure P g Measuring the pressure P of the inlet chamber m The values of the variation over time t are then calculated as the respective gettering rate (S) and gettering capacity (Q) of the material.
As can be seen from the phase diagram, the main phase in ZrAl1 is an alpha-Zr solid solution, and a very small amount of Zr is contained 3 Al is difficult to obtain granular alloy powder by directly adopting a conventional mechanical pulverizing method because the ductility of the alpha-Zr solid solution is good. Further, no zral1 powder is commercially available, and no method for producing zral1 powder is reported in the literature. The invention provides a preparation method and application of high-purity ZrAl1 powder, aiming at the defects or the shortcomings of the existing high-purity ZrAl1 powder preparation technology.
A preparation method of high-purity ZrAl1 powder comprises the following steps:
(1) Preparing a ZrAl1 alloy ingot by adopting a crucible-free suspension smelting method so as to ensure the purity of the ingot; vacuum-pumping the smelting cavity to 10 before smelting -2 Pa magnitude, then filling high-purity Ar, and repeatedly flushing for 2-3 times; in order to ensure the components to be uniform, the suspension smelting times of each ZrAl1 alloy ingot are 3 to 4 times;
(2) ZrAl1 powder as a reducing agent is an active material, is extremely easy to oxidize in the crushing process, and adopts a hydrogenation dehydrogenation method to prepare alloy powder. Firstly, polishing to remove oxides and the like on the surface of the ZrAl1 alloy ingot, and carrying out opening treatment by using a saw. The ZrAl1 alloy ingot is put into a hydrogenation dehydrogenation furnace, and the hydrogenation dehydrogenation furnace is used for high-purity H before vacuumizing 2 Flushing for 2-4 times, vacuumizing until the air pressure of the cavity is less than 1X 10 -4 Heating the alloy ingot to 300-500 ℃ and preserving heat for 1-2 h to activate the alloy ingot, then filling hydrogen, wherein the pressure of the hydrogen filled in each time is 0.2-0.5 MPa, and filling hydrogen again when the pressure drop of the hydrogen in the furnace is 0.01-0.04 MPa, repeating the hydrogen filling for 5-8 times, starting cooling after the pressure drop of the hydrogen in the furnace is 0.01-0.04 MPa after the last hydrogen filling, and filling high-purity Ar with the pressure of more than 0.1MPa and less than 0.5MPa into the hydrogenation dehydrogenation furnace after the temperature is reduced to 100-200 ℃;
(3) Taking out the ZrAl1 alloy ingot obtained in the step (2), and crushing and sieving by adopting a conventional machine; when screening, screens with different apertures are used according to the required granularity range, such as-80 to +300 meshes, -150 to +250 meshes or-300 meshes, and the like, high-purity Ar gas is filled into the screens for protection, then a vibrating screen is adopted to screen ZrAl1 alloy powder with the required granularity, and the vibrating screen time is 1-3 min.
(4) Carrying out dehydrogenation treatment on the ZrAl1 alloy powder obtained in the step (3) for 1-3 times; the obtained ZrAl1 alloy powder is flatly laid in a molybdenum box, and is filled in a hydrogenation dehydrogenation furnace, when the chamber pressure is less than 1 multiplied by 10 -4 In Pa, the powder is heated, the dehydrogenation treatment temperature is 500-700 ℃, the heat preservation time is 0.5-1.5 hours, and the powder needs to be sieved again after each dehydrogenation treatment.
(5) And (3) vacuumizing and packaging the ZrAl1 powder obtained in the step (4) for standby.
The prepared high-purity ZrAl1 powder is used as a reducing agent of a sodium source, is used for reducing sodium salt to generate sodium metal vapor, and is used for absorbing active impurity gas, wherein the active impurity gas is one or more mixed gases of hydrogen, oxygen, nitrogen, water vapor, carbon monoxide and carbon dioxide.
Example 1
Zirconium iodide (99.95%) and refined aluminum (99.99%) are used as raw materials, 401.39g of the raw materials are prepared according to 99wt.% of Zr and 1wt.% of Al, a ZrAl1 alloy ingot is prepared by suspension smelting, and a smelting cavity is vacuumized to 10% before smelting -2 And (3) filling high-purity Ar (argon) for repeatedly flushing for 3 times, and repeatedly smelting for 3 times on the front side and the back side to ensure uniform components.
The surface of the suspension-melted ingot is polished for oxides or the like, and then the opening is sawn with a saw, which may be cross-shaped. Loading the alloy ingot into a hydrogenation and dehydrogenation furnace, and using high-purity H in the hydrogenation and dehydrogenation furnace before vacuumizing 2 Flushing 3 times when the chamber pressure is less than 1X 10 -4 At Pa, the alloy ingot is heated and incubated at 400 ℃ for 1.5h to activate the ZrAl1 ingot. And then charging hydrogen, namely charging hydrogen again for 6 times when the pressure drop of hydrogen is 0.02MPa and the pressure of hydrogen in the furnace is 0.02MPa after the last charging, starting to cool down, cooling to 120 ℃, and introducing high-purity Ar with the pressure of 0.2MPa into the hydrogenation dehydrogenation furnace. And cooling the powder to room temperature, taking out the powder, sieving out-80- +300 mesh powder by using a sieving machine, and filling high-purity Ar gas into a screen for protection, wherein the sieving time is 2min. The powder was then subjected to 2 dehydrogenations. When the chamber pressure is less than 1 x 10 -4 In Pa, the powder is heated, the dehydrogenation treatment temperature is 600 ℃, the heat preservation time is 1.0 hour, and the powder needs to be sieved again after each dehydrogenation treatment.
The particle size distribution D of the obtained-80- +300 mesh ZrAl1 alloy powder 10 ＝71.856μm，D 50 ＝143.782μm，D 90 = 265.440 μm. The purity of the obtained ZrAl1 alloy powder was 99.88%, wherein the content of each element was (wt.%): zr 98.96, al 1.08, cu<0.001, H0.014, O0.11, i.e., high powder purity, low hydrogen and oxygen content, indicated that the dehydrogenation treatment was sufficient.
FIG. 1 is an XRD pattern of ZrAl1 alloy powder, showing that ZrAl1 alloy mainly consists of a solid solution phase of alpha-Zr with close-packed hexagonal structure, and that the diffraction peak of the solid solution of alpha-Zr is not caused to deviate from that of pure metal of alpha-Zr because the content of Al is low and the atomic radius of Al (143 pm) is not much different from that of Zr (160 pm). The two very low diffraction peaks at diffraction angles of 32-33℃may be associated with very small amounts of other phases such as Zr 3 The presence of Al is relevant. No other impurity phases were present in the XRD pattern. The alpha-Zr solid solution is an air suction phase, is beneficial to absorbing other impurity gases emitted when sodium metal vapor is released, and improves the purity of the sodium metal vapor.
Example 2
Examples are employed1, sieving out powder with-300 meshes by using a vibrating sieve, and filling high-purity Ar gas into a screen for protection, wherein the vibrating sieve time is 2min. The powder was then subjected to 2 dehydrogenations. When the chamber pressure is less than 1 x 10 -4 In Pa, the powder is heated, the dehydrogenation treatment temperature is 600 ℃, the heat preservation time is 1.0 hour, and the powder needs to be sieved again after each dehydrogenation treatment.
The particle size distribution of the obtained powder of-300 meshes is D 10 ＝11.086μm，D 50 ＝30.476μm，D 90 = 62.175 μm. The purity of the obtained ZrAl1 alloy powder was 99.66%, wherein the content of each element was (wt.%): zr 99.05, al 1.19, cu<0.001, H0.019 and O0.32. It can be seen from examples 1 and 2 that the ingot produced by suspension smelting has a relatively uniform distribution of ingredients and is quite similar in powder composition of different particle sizes; the powder purity was better than 99.5% taking into account the oxygen content of the powder. Because of the fine granularity of the powder of-300 meshes, the oxygen content in the powder is higher than that of-80 to +300 meshes.
The sensitivity of the photosensitive surface may be altered by the gaseous material deposited on the surface. The main residual gas in the image tube is N 2 、O 2 、CO 2 、CO、CH 4 、C 2 H 4 、H 2 O、H 2 Inert gases such as Ar and He. The residual gas collides with photoelectrons to generate positive ions when the image intensifier tube works, and the positive ions bombard the photocathode under the action of an accelerating electric field to change the surface of the photocathode, so that the sensitivity is reduced. While photoelectrons or secondary electrons inside the tube bombard the cone electrode or the insulating part of the tube at a high speed to release harmful gases, especially O 2 Steam, etc., will affect the chemical stability of the photocathode, causing a decrease in the photocathode sensitivity.
The high-purity ZrAl1 powder is used as a reducing agent in a sodium source to reduce sodium metal salt to release sodium metal vapor, and is also used as a getter to absorb active impurity gas, so that the purity of the sodium metal vapor is improved, and the sensitivity of the photocathode is improved.
0.6g-300 meshes of ZrAl1 powder is pressed into a round piece with the diameter of 10.45mm under the pressing pressure of 420MPa, and the round piece is tested at 350The room temperature hydrogen absorption performance after being activated under the activation condition of heat preservation for 30min at the temperature is tested to be P by adopting a constant pressure method g ＝2.7×10 -4 Pa. FIG. 2 is a graph showing the results of hydrogen absorption performance test of ZrAl1 alloy powder, wherein the initial hydrogen absorption rate is higher than 850 ml/s.g, and the accumulated hydrogen absorption amount of 120min is higher than 1150 Pa.ml/g, which shows that the ZrAl1 alloy powder has better hydrogen absorption performance after being activated at low temperature. In addition, zrAl1 powder was also tested for CO and N 2 The result shows that the absorption performance of the catalyst is better for CO and N at room temperature 2 Also has certain absorption performance.
Example 3
As in example 1, a ZrAl1 alloy ingot was prepared by suspension melting, and the mass of the batch was 399.06g. The surface of the suspension-melted ingot is polished for oxides or the like, and then the opening is sawed with a saw. Loading the alloy ingot into a hydrogenation and dehydrogenation furnace, and using high-purity H in the hydrogenation and dehydrogenation furnace before vacuumizing 2 Flushing 4 times when the chamber pressure is less than 1X 10 -4 At Pa, the alloy ingot is heated and incubated at 500℃for 1.0h to activate the ZrAl1 ingot. And then charging hydrogen, wherein the hydrogen pressure is 0.45MPa each time, charging hydrogen again when the hydrogen pressure drop is 0.03MPa, charging hydrogen for 7 times in total, starting to cool after the hydrogen pressure drop is 0.03MPa after the last time of charging hydrogen, and introducing high-purity Ar with the pressure of 0.15MPa into the hydrogenation dehydrogenation furnace after cooling to 150 ℃. And cooling the powder to room temperature, taking out the powder, sieving out-80- +300 mesh powder by using a sieving machine, and filling high-purity Ar gas into a screen for protection, wherein the sieving time is 3min. The powder was then subjected to 2 dehydrogenations. When the chamber pressure is less than 1 x 10 -4 In Pa, the powder is heated, the dehydrogenation treatment temperature is 700 ℃, the heat preservation time is 45 minutes, and the powder needs to be sieved again after each dehydrogenation treatment.
The particle size distribution D of the ZrAl1 alloy powder with the particle size of-80 to +300 meshes is obtained 10 ＝73.666μm，D 50 ＝144.570μm，D 90 = 261.861 μm. The purity of the obtained ZrAl1 alloy powder was 99.87%, wherein the content of each element was (wt.%): zr 99.02, al 1.17, cu<0.001, H0.016, O0.11, i.e. high powder purity, low hydrogen and oxygen content. From examples 1 and 3 it can be seen that the composition of ingots of different batches prepared by suspension smelting is essentiallyAnd consistent.
FIG. 3 shows the morphology of a-300 mesh ZrAl1 alloy powder prepared by a hydrogenation dehydrogenation method, which can be seen as polyhedral irregular particles.
Example 4
The powder after hydrogen absorption in example 3 was used to screen the powder, high purity Ar gas was charged into the screen for protection, the shaking time was 3min, and powder of-150 to +250 mesh was obtained, particle size distribution D 10 ＝73.906μm，D 50 ＝108.407μm，D 90 = 158.519 μm. The powder was then subjected to 3 dehydrogenations. When the chamber pressure is less than 1 x 10 -4 In Pa, the powder is heated, the dehydrogenation treatment temperature is 700 ℃, the heat preservation time is 1.2 hours, and the powder needs to be sieved again after each dehydrogenation treatment. The purity of the obtained ZrAl1 alloy powder was 99.81%, wherein the content of each element was (wt.%): zr 98.98, al 1.11, cu<0.001、H 0.012、O 0.18。
The foregoing description of the preferred embodiments of the invention is merely illustrative of the invention and is not intended to be limiting. It should be noted that, for those skilled in the art, other equivalent modifications can be made in light of the technical teaching provided by the present invention, and the present invention can be implemented as the scope of protection.

Claims (6)

1. The preparation method of the high-purity ZrAl1 powder is characterized by comprising the following steps of:
(1) Preparing a ZrAl1 alloy ingot by adopting a suspension smelting method; in the step (1), the smelting cavity is vacuumized to 10 before smelting -2 Pa magnitude, then filling high-purity Ar, and repeatedly flushing for 2-3 times; the suspension smelting times of the ZrAl1 alloy ingot prepared by adopting the suspension smelting method are 3-4 times;
(2) The ZrAl1 alloy ingot is put into a hydrogenation dehydrogenation furnace and vacuumized until the air pressure in the cavity is less than 1 multiplied by 10 -4 Heating the alloy ingot to 300-500 ℃ and preserving heat for 1-2 h under Pa, then charging hydrogen gas with the pressure of 0.2-0.5 MPa, charging hydrogen gas again under the pressure drop of 0.01-0.04 MPa in the furnace, repeating charging for 5-8 times, and cooling to 10 ℃ after the pressure drop of 0.01-0.04 MPa in the furnaceAfter the temperature is between 0 and 200 ℃, introducing high-purity Ar with the pressure being more than 0.1MPa and less than 0.5MPa into the furnace;
(3) Taking out the ZrAl1 alloy ingot obtained in the step (2), and mechanically crushing and screening;
(4) Carrying out dehydrogenation treatment on the ZrAl1 alloy powder obtained in the step (3) for 1-3 times; the step (4) of dehydrogenation treatment is to lay the obtained ZrAl1 alloy powder in a molybdenum box, and put the molybdenum box into a hydrogenation dehydrogenation furnace, when the air pressure in the chamber is less than 1 multiplied by 10 -4 In Pa, heating the powder, wherein the dehydrogenation treatment temperature is 500-700 ℃, the heat preservation time is 0.5-1.5 hours, and sieving the powder again is needed after each dehydrogenation treatment;
(5) And (3) vacuumizing and packaging the ZrAl1 powder obtained in the step (4) for standby.
2. The method according to claim 1, wherein in the step (2), the ZrAl1 alloy ingot is charged into a hydrogenation and dehydrogenation furnace, oxides on the surface of the ZrAl1 alloy ingot are removed, and an opening treatment is performed.
3. The process according to claim 1, wherein the hydrogenation/dehydrogenation furnace is subjected to high purity H before the vacuum is applied in the step (2) 2 Flushing for 2-4 times.
4. The preparation method of the alloy powder according to claim 1, wherein the high-purity Ar gas is filled into the screen mesh adopted in the step (3) for protection, and then ZrAl1 alloy powder with the required granularity is screened out by a screen shaker for 1-3 min.
5. A high purity ZrAl1 powder prepared by the method according to any one of claims 1 to 4, wherein the high purity ZrAl1 powder is used as a reducing agent for sodium source and for absorbing active impurity gas.
6. The high purity ZrAl1 powder according to claim 5, wherein the active impurity gas is one or more mixed gases selected from the group consisting of hydrogen, oxygen, nitrogen, steam, carbon monoxide and carbon dioxide.
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