CN108165824A - A kind of hydrogen adsorbing alloy under ultralow pressure environment without activation and preparation method thereof - Google Patents
A kind of hydrogen adsorbing alloy under ultralow pressure environment without activation and preparation method thereof Download PDFInfo
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- CN108165824A CN108165824A CN201711426262.4A CN201711426262A CN108165824A CN 108165824 A CN108165824 A CN 108165824A CN 201711426262 A CN201711426262 A CN 201711426262A CN 108165824 A CN108165824 A CN 108165824A
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- hydrogen
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- activation
- melting
- hydrogen adsorbing
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C2202/00—Physical properties
- C22C2202/04—Hydrogen absorbing
Abstract
The present invention relates to a kind of hydrogen adsorbing alloy under ultralow pressure environment without activation and preparation method thereof, chemical element composition and its Zr, 30 ~ 40% V, 1 ~ 6% Fe, 1 ~ 6% M that stoichiometric atomic mole (mol) percentage is 55 ~ 65%,（M is any one of Cr, Mn）.The specific process step of preparation method is as follows：Dispensing is according to chemical formula Zr57V36Fe7‑xMxIngredient and above-mentioned stoichiometric atomic mole (mol) percentage in (X=1 ~ 6) carry out dispensing.With vacuum magnetic control tungsten electrode arc furnace, melting is uniform under protection of argon gas for melting, applies electromagnetic agitation in fusion process, is smelted into alloy pig.Alloy prepared by this method, operating process is simple, can absorb hydrogen under ultra low pressure at room temperature without activation, dehydrogenation is with good application prospect in the vacuum equipment of non-refractory.
Description
Technical field
It is prepared under ultralow pressure environment with vacuum magnetic control tungsten electrode arc smelting furnace the present invention relates to a kind of, particularly hydrogen atom
In clock after the state selection of magnetic field F=0, m=1 and F=1, the absorption of the energy level hydrogen atom of m=1, the hydrogen adsorbing alloy Zr without activation-V-Fe-
M-（M is transition element）Specific method.
Background technology
With the continuous extension of vacuum technique application field, non evaporable getter material is as a kind of special active material
It is more and more widely used.And application level of the vacuum technique in vacuum device is improved, it is to develop long-life, Gao Ke
It leans on, one of the key of excellent performance device.With the rapid development of science and technology and defence and military cause, to special vacuum device
Higher and higher with gettering material requirement, the vacuum device especially applied under hydrogen environment is not required nothing more than to hydrogen
There is big uptake, also requirement has big hydrogen-absorption speed and low activationary temperature.And current material can not fully meet this
A little requirements.Main problem existing for hydrogen adsorbing alloy is at present：1st, activationary temperature is high, and hydrogen-absorbing material at present will pass through 400 DEG C
Suction hydrogen could be carried out after above activation, so as to can pair material proposition mechanical behavior under high temperature to match with it and non-deformability
It is required that thermal damage can be caused to vacuum device, so as to influence the service life of vacuum device when secondly heating.2nd, hydrogen-absorption speed exists
It is difficult to meet the requirements in certain applications, so as to influence the vacuum degree of system.So developing, a kind of activationary temperature is low, hydrogen-absorption speed
Soon, the big hydrogen adsorbing alloy of hydrogen-sucking amount is always the striving direction of researcher.
Invention content
The object of the present invention is to provide a kind of hydrogen adsorbing alloys under ultralow pressure environment without activation and preparation method thereof（This
Invention is in National Natural Science Foundation of China-Chinese Academy of Sciences's astronomy joint fund assistance（U1531120）Lower completion）.It should
Technological operation is simple, convenient for industrialized production.The hydrogen adsorbing alloy of the present invention is a kind of Zr-V-Fe-M alloys of crystalline state, it keeps
The characteristics of the advantages of zirconium hydrogen-sucking amount is big, vanadium reduces activationary temperature, but overcome existing hydrogen adsorbing alloy must be sharp at more than 400 DEG C
The characteristics of living low with hydrogen-absorption speed, can absorb a large amount of hydrogen at room temperature and hydrogen-absorption speed is fast.
The present invention adopts the following technical scheme that technical process and step are as follows：
A. dispensing：Using stoichiometric atomic mole (mol) percentage as：
55 ~ 65 % sponge Zr,
30 ~ 40 % metal V,
0 ~ 10 % metal Fe,
0 ~ 10 % metals M；
M is any one of transition element Cr, Mn.The purity of raw material is the % of 99.95 % ~ 99.99；
B. melting：Sample room is first extracted into 3 × 10 using vacuum magnetic control tungsten electrode arc furnace-3Pa is passed through Ar (argon) gas extremely
0.01 MPa, then it is evacuated to 3 × 10-3 Pa is re-filled with Ar (argon) gas to 0.01 MPa, under protection of argon gas, melting 4
All over so that alloy is uniformly mixed；It often refines one time and overturns spindle；Apply magnetic stirring after melting at twice, magnetic mixing time is 60
S is smelted into alloy pig；The theoretical density of hydrogen adsorbing alloy is made to reach 100 %.
The preparation method of the hydrogen adsorbing alloy of the present invention, features and advantages are by preset stoichiometric atomic mole
(mol) percentage prepares hydrogen adsorbing alloy by vacuum arc melting.Its technological operation is simple, and the hydrogen adsorbing alloy of acquisition is without living
Change can absorb hydrogen under ultra low pressure at room temperature and hydrogen sucking function is excellent, it is easy to accomplish industrialized production, intolerant to height
Dehydrogenation has good effect in the vacuum equipment of temperature.
Description of the drawings
Fig. 1 is the XRD spectrum of the embodiment of the present invention one.
Fig. 2 is the Dynamic isotherms of hydrogen absorption of the embodiment of the present invention one.
Fig. 3 is the XRD spectrum of the embodiment of the present invention two.
Fig. 4 is the Dynamic isotherms of hydrogen absorption of the embodiment of the present invention two.
Fig. 5 is the XRD spectrum of the embodiment of the present invention three.
Fig. 6 is the Dynamic isotherms of hydrogen absorption of the embodiment of the present invention three.
Specific embodiment
Details are as follows for the preferred embodiment of the present invention combination attached drawing：
Embodiment 1
The chemical general formula of hydrogen adsorbing alloy is Zr57V36Fe7-xMxIn formula：When M=Cr, x=3, Zr is formed57V36Fe4Cr3Alloy, specifically
Step is as follows：
A. stoichiometrically atomic molar (mol) percentage carries out dispensing, and it is 99.99 % that the purity of raw material, which is Zr, and V is
99.95 %, Fe are 99.95 %, and Cr is 99.98 %.
B. raw material is placed in vacuum magnetic control tungsten electrode arc smelting furnace, is evacuated to 3 × 10-3Pa is passed through Ar (argon) gas
To 0.01 MPa, then it is evacuated to 3 × 10-3 Pa is re-filled with Ar (argon) gas to 0.01 MPa, and melting 4 times is so that alloy
It is uniformly mixed, often refines one time and overturn spindle, apply magnetic stirring after melting at twice, magnetic mixing time is 60 S, is obtained
Zr57V36Fe4Cr3Alloy pig.
C. melted ingot casting is cut into sheet by wire cutting, sanding and polishing tests XRD spectrum such as Fig. 1 institutes later
Show, mainly by α-Zr phases and ZrV before suction hydrogen2Phase composition.
D. about 0.5 g of the alloy is placed in PCI testers, takes out 2 h vacuum, room temperature（25℃）Under, test its suction
Hydrogen amount, for the Dynamic isotherms of hydrogen absorption of gained hydrogen adsorbing alloy as shown in Fig. 2, total hydrogen-sucking amount is 2.21 wt.%.
Embodiment 2
The chemical general formula of hydrogen adsorbing alloy is Zr57V36Fe7-xMxIn formula：When M=Cr, x=6, Zr is formed57V36Fe1Cr6Alloy, specifically
Step is as follows：
A. stoichiometrically atomic molar (mol) percentage carries out dispensing, and it is 99.99 % that the purity of raw material, which is Zr, and V is
99.95 %, Fe are 99.95 %, and Cr is 99.98 %.
B. raw material is placed in vacuum magnetic control tungsten electrode arc smelting furnace, is evacuated to 3 × 10-3Pa is passed through Ar (argon) gas
To 0.01 MPa, then it is evacuated to 3 × 10-3 Pa is re-filled with Ar (argon) gas to 0.01 MPa, and melting 4 times is so that alloy
It is uniformly mixed, often refines one time and overturn spindle, apply magnetic stirring after melting at twice, magnetic mixing time is 60 S, is obtained
Zr57V36Fe1Cr6Alloy pig.
C. melted ingot casting is cut into sheet by wire cutting, sanding and polishing tests XRD spectrum such as Fig. 3 institutes later
Show, mainly by α-Zr phases and ZrV before suction hydrogen2Phase composition.
D. about 0.5 g of the alloy is placed in PCI testers, takes out 2 h vacuum, room temperature（25℃）Under, test its suction
Hydrogen amount, for the Dynamic isotherms of hydrogen absorption of gained hydrogen adsorbing alloy as shown in Fig. 4, total hydrogen-sucking amount is 2.24 wt.%.
Embodiment 3
The chemical general formula of hydrogen adsorbing alloy is Zr57V56Fe7-xMxIn formula：When M=Mn, x=3, Zr is formed57V36Fe4Mn3Alloy, specifically
Step is as follows：
A. stoichiometrically atomic molar (mol) percentage carries out dispensing, and it is 99.99 % that the purity of raw material, which is Zr, and V is
99.95 %, Fe are 99.95 %, and Mn is 99.99 %.
B. raw material is placed in vacuum magnetic control tungsten electrode arc smelting furnace, is evacuated to 3 × 10-3Pa is passed through Ar (argon) gas
To 0.01 MPa, then it is evacuated to 3 × 10-3 Pa is re-filled with Ar (argon) gas to 0.01 MPa, and melting 4 times is so that alloy
It is uniformly mixed, often refines one time and overturn spindle, apply magnetic stirring after melting at twice, magnetic mixing time is 60 S, is obtained
Zr57V36Fe4Mn3Alloy pig.
C. melted ingot casting is cut into sheet by wire cutting, sanding and polishing tests XRD spectrum such as Fig. 5 institutes later
Show, mainly by α-Zr phases and ZrV before suction hydrogen2Phase composition.
D. about 0.5 g of the alloy is placed in PCI testers, takes out 2 h vacuum, room temperature（25℃）Under, test its suction
Hydrogen amount, for the Dynamic isotherms of hydrogen absorption of gained hydrogen adsorbing alloy as shown in Fig. 6, total hydrogen-sucking amount is 2.18 wt.%.
By more than case study on implementation and its corresponding XRD spectrum and test curve it is found that in Zr-V-Fe-M-In alloy, close
Golden is all mainly by α-Zr phases and ZrV2Phase composition, the hydrogen-sucking amount of three embodiments is respectively 2.21 wt.%, 2.24 at room temperature
wt.%、2.18 wt.%（Being converted into hydrogen-sucking amount under standard state is respectively：246.9 L/kg、250.93 L/kg、242.65 L/
Kg）, gettering rate respectively reaches 3.9ml*s in 60 s-1*g-1、4 ml*s-1*g-1, 3.6 ml*s-1*g-1With good suction hydrogen
Behavior.This alloy can absorb hydrogen, and hydrogen-absorption speed is fast without activation under ultra low pressure, and hydrogen-sucking amount is big, have excellent
Hydrogen sucking function.
Claims (2)
1. a kind of hydrogen adsorbing alloy under ultralow pressure environment without activation, it is characterised in that：It is formed with following chemical element
And its stoichiometric atomic mole (mol) percentage：
55 ~ 65 % of Zr,
30 ~ 40 % of V,
1 ~ 6 % of Fe,
M 1~6 %；
M is any one of Cr, Mn.
2. a kind of preparation method under ultralow pressure environment without the hydrogen adsorbing alloy of activation, it is characterised in that：With following work
Skill process and step：
A), dispensing：Dispensing is carried out according to above-mentioned raw materials formula, and the purity of raw material is the % of 99.95 % ~ 99.99；
B), melting：Using vacuum magnetic control tungsten electrode arc, sample room is first extracted into 3 × 10-3Pa is passed through Ar (argon) gas to 0.01
MPa, then it is evacuated to 3 × 10-3 Pa is re-filled with Ar (argon) gas to 0.01 MPa, under protection of argon gas, melting 4 times so that
Alloy is uniformly mixed；It often refines one time and overturns spindle；Apply magnetic stirring after melting at twice, magnetic mixing time is 60 S, is melted
It is smelt alloy pig；The theoretical density of hydrogen adsorbing alloy is made to reach 100 %.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4839085A (en) * | 1987-11-30 | 1989-06-13 | Ergenics, Inc. | Method of manufacturing tough and porous getters by means of hydrogen pulverization and getters produced thereby |
| CN102383068A (en) * | 2011-10-09 | 2012-03-21 | 上海大学 | Amorphous state hydrogen absorption alloy having mechanical property and preparation method thereof |
-
2017
- 2017-12-26 CN CN201711426262.4A patent/CN108165824A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4839085A (en) * | 1987-11-30 | 1989-06-13 | Ergenics, Inc. | Method of manufacturing tough and porous getters by means of hydrogen pulverization and getters produced thereby |
| CN102383068A (en) * | 2011-10-09 | 2012-03-21 | 上海大学 | Amorphous state hydrogen absorption alloy having mechanical property and preparation method thereof |
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Application publication date: 20180615 |