CN105369068B - La Mg Ni hydrogen bearing alloys and preparation method thereof - Google Patents
La Mg Ni hydrogen bearing alloys and preparation method thereof Download PDFInfo
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- CN105369068B CN105369068B CN201510819838.8A CN201510819838A CN105369068B CN 105369068 B CN105369068 B CN 105369068B CN 201510819838 A CN201510819838 A CN 201510819838A CN 105369068 B CN105369068 B CN 105369068B
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
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Abstract
It is a primary object of the present invention to provide a kind of La Mg Ni hydrogen bearing alloys and preparation method thereof.The preparation method comprises the following steps：The mixed-metal feedstock prepared in proportion is subjected to melting, obtains liquid alloy；Liquid alloy spray is fallen and quickly cooled down on chill roll, obtains alloy after fast quenching, the wherein linear resonance surface velocity of chill roll is 3~8m/s；Alloy after fast quenching is heat-treated, included the step of heat treatment：Under the protection of inert gas, 1~2 hour first is incubated at 500~600 DEG C, then 1~2 hour is incubated at 700~800 DEG C, is finally incubated 2~6 hours at 800~900 DEG C.A with single type can be obtained using above-mentioned preparation method2B7The La Mg Ni hydrogen bearing alloys of phase.Simultaneously as the crystal grain of alloy is tiny after fast quenching, transition kinetics are very fast, shorter annealing time can be used to obtain single A2B7The La Mg Ni hydrogen bearing alloys of phase.In addition, this method is easy to grasp, it is adapted to large-scale production.
Description
Technical field
The invention belongs to hydrogen storage material technical field, in particular to a kind of La-Mg-Ni hydrogen bearing alloys and its preparation
Method.
Background technology
As nickel-hydrogen battery negative pole material of new generation, La-Mg-Ni (3≤B/A ＜ 5) hydrogen bearing alloys in discharge capacity and
All more traditional AB on high power discharge capability5Type alloy possesses bigger potentiality.However, La-Mg-Ni hydrogen bearing alloys follow in electrochemistry
The fast decay of capacity is the maximum bottleneck for limiting its application during ring.Therefore, how high power capacity and multiplying power discharging are being ensured
Electrochemical cycle stability is improved on the premise of ability, turns into the key that this is alloy exploitation.
Research shows that the major reason of La-Mg-Ni alloys failure is the corrosion that alloy occurs in alkaline solution.From material
From the perspective of expecting Corrosion Science, it is the important channel for improving alloy corrosion resistance to obtain homogeneous structure.Contain in La-Mg-Ni systems
There is multiple compounds phase, AB can be formed by being up to the present reported in La-Mg-Ni systems2、AB3、A2B7、A5B19、AB5Type phase
And the A being not present in binary system6B24Type phase.In all heterogeneous structure types, A2B7Type is mutually found to have higher electric discharge
Ability and excellent cyclical stability.Therefore, A is improved as far as possible2B7The content of type phase even obtains the A of single type2B7Type structure
It is the key that further raising La-Mg-Ni should be alloy cyclical stability.
However, using conventional method of smelting, La-Mg-Ni system alloys generally comprise more than three kinds of phase structure.Although
Annealing can significantly improve A2B7The content of type phase, but the A of single type2B7Type is mutually difficult to obtain.Particularly AB5Type phase
Fusing point is higher, is difficult to decompose, even if being still difficult to eliminate by long heat treatment.
For example, the Chinese patent of Publication No. 101353733 discloses a kind of preparation method of La-Mg-Ni hydrogen bearing alloys,
Including：The alloy of preparation is put into melting in the copper crucible of the lower high frequency suspension smelting furnace of argon gas protection, melt back is three times；Will be upper
The alloy that step obtains is heat-treated, and condition is to be warming up to 800~1000 DEG C, is incubated 4-24 hours, obtains containing a small amount of LaNi5
The La of phase2Ni7The alloy of type.
In another example Publication No. 10228668A Chinese patent discloses a kind of Mg base hydrogen bearing alloy, by Mg, Ni and Mm
Three kinds of components composition, wherein and Mm be made up of Ce and La, the Mg base hydrogen bearing alloy is prepared by following steps：By Ni and Mm
First melting prepares prealloy, then heating-up temperature be magnesium fusing point more than by the prealloy fragmentation of preparation after felt again with Mg
Melting is answered, to obtain the Mg base hydrogen bearing alloy of Mg base hydrogen bearing alloy.However, the Mg base hydrogen bearing alloy that this method is prepared includes
Mg、Mg2Ni and MmMg12Three thing phases.
Therefore, single A how is prepared2B7The La-Mg-Ni hydrogen bearing alloys of type phase, and make that its processing step is simple, consumption
When requirement that is short and reaching industrialized scale, turn into technical barrier urgently to be resolved hurrily at present.
The content of the invention
It is single to obtain it is a primary object of the present invention to provide a kind of La-Mg-Ni hydrogen bearing alloys and preparation method thereof
A2B7The La-Mg-Ni hydrogen bearing alloys of type phase.
To achieve these goals, according to an aspect of the invention, there is provided a kind of system of La-Mg-Ni hydrogen bearing alloys
Preparation Method, the preparation method comprise the following steps：The mixed-metal feedstock prepared in proportion is subjected to melting, obtains liquid conjunction
Gold；Liquid alloy spray is fallen and quickly cooled down on chill roll, obtains the linear resonance surface velocity of alloy after fast quenching, wherein chill roll
For 3~8m/s；Alloy after fast quenching is heat-treated, included the step of heat treatment：Under the protection of inert gas, first 500
1~2 hour is incubated at~600 DEG C, then 1~2 hour is incubated at 700~800 DEG C, 2~6 are finally incubated at 800~900 DEG C
Hour.
Further, the step of mixed-metal feedstock being carried out into melting includes：0.01 is filled with to vacuum induction melting furnace~
0.1MPa inert gas；Mixed-metal feedstock is melted at a temperature of 1573K~1873K afterwards, and kept for 1~5 minute.
Further, the step of being filled with 0.01~0.1MPa inert gas includes：Vacuum induction melting furnace is vacuumized
To 1 × 10-4Below Pa, inert gas is filled with to normal pressure；1 × 10 is evacuated to again-4Below Pa, and it is filled with 0.01~
0.1MPa inert gas.
Further, alloy includes AB after fast quenching2Type phase, AB3Type phase, A2B7Type phase and AB5Type phase, wherein AB5Type phase
Volume content is less than 20%.
Further, the crystallite dimension of alloy is 2~10 μm after fast quenching.
Further, in the step of heat treatment, charged pressure is less than 0.1MPa inert gas.
Further, the chemical formula of La-Mg-Ni hydrogen bearing alloys is La2-xMgxNi7, wherein 0.2≤x≤0.5；La-Mg-Ni
Hydrogen bearing alloy is by A2B7Type phase composition.
According to another aspect of the present invention, present invention also offers a kind of La-Mg-Ni hydrogen bearing alloys, La-Mg-Ni storages
Hydrogen alloy above-mentioned preparation method provided by the present invention is made.
According to another aspect of the invention, present invention also offers a kind of La-Mg-Ni hydrogen bearing alloys, La-Mg-Ni storages
Hydrogen alloy is by single A2B7Type phase composition.
Low speed quick-quenching method is by AB during the present invention uses5The content of type phase suppresses in appropriate scope, while obtains composition
With alloy after the fast quenching of even tissue, then using stage annealing process, insulation is stopped respectively in low temperature to high temperature section, is made fast
Low melting point phase and high-melting-point after quenching in alloy are mutually undergone phase transition successively, so as to obtain the A of single type2B7Type phase.Meanwhile by
The crystal grain of alloy is tiny after fast quenching, and transition kinetics are very fast, shorter annealing time can be used to obtain single A2B7Type
The La-Mg-Ni hydrogen bearing alloys of phase.In addition, this method is easy to grasp, it is adapted to large-scale production.
Brief description of the drawings
The Figure of description for forming the part of the application is used for providing a further understanding of the present invention, and of the invention shows
Meaning property embodiment and its illustrate be used for explain the present invention, do not form inappropriate limitation of the present invention.In the accompanying drawings：
Fig. 1 shows the flow signal of the preparation method for the La-Mg-Ni hydrogen bearing alloys that embodiment of the present invention is provided
Figure；
Fig. 2 shows the metallographic structure of alloy after the fast quenching that embodiment 1 obtains；
Fig. 3 shows the XRD spectrum of alloy after the fast quenching that embodiment 1 obtains；
Fig. 4 a show the metallographic structure for the La-Mg-Ni hydrogen bearing alloys that embodiment 1 obtains；
Fig. 4 b show the metallographic structure (backscattered electron image figure) for the La-Mg-Ni hydrogen bearing alloys that embodiment 1 obtains；
Fig. 4 c show the power spectrum Surface scan distribution map of 3 kinds of elements in the La-Mg-Ni hydrogen bearing alloys that embodiment 1 obtains；
Fig. 5 shows the XRD spectrum for the La-Mg-Ni hydrogen bearing alloys that embodiment 1 obtains.
Embodiment
It should be noted that in the case where not conflicting, the feature in embodiment and embodiment in the application can phase
Mutually combination.Describe the application in detail below with reference to the accompanying drawings and in conjunction with the embodiments.
It should be noted that term used herein above is merely to describe embodiment, and be not intended to restricted root
According to the illustrative embodiments of the application.As used herein, unless the context clearly indicates otherwise, otherwise singulative
It is also intended to include plural form, additionally, it should be understood that, when in this manual using term "comprising" and/or " bag
Include " when, it indicates existing characteristics, step, operation, device, component and/or combinations thereof.
The present inventor provides a kind of preparation method of La-Mg-Ni hydrogen bearing alloys.As shown in figure 1, the preparation side
Method comprises the following steps：The mixed-metal feedstock prepared in proportion is subjected to melting, obtains liquid alloy；Liquid alloy spray is fallen
Quickly cooled down on chill roll, obtain alloy after fast quenching, the wherein linear resonance surface velocity of chill roll is 3~8m/s；By fast quenching
Alloy is heat-treated afterwards, is included the step of heat treatment：Under the protection of inert gas, 1~2 is first incubated at 500~600 DEG C
Hour, then 1~2 hour is incubated at 700~800 DEG C, finally it is incubated 2~6 hours at 800~900 DEG C.
Low speed quick-quenching method is by AB during above-mentioned preparation method uses5The content of type phase suppresses, in appropriate scope, to obtain simultaneously
Alloy after the fast quenching of composition and even tissue, then using stage annealing process, guarantor is stopped respectively in low temperature to high temperature section
Temperature, the low melting point phase after fast quenching in alloy and high-melting-point is set mutually to undergo phase transition successively, so as to obtain the A of single type2B7Type phase.
That is, the La-Mg-Ni hydrogen bearing alloys prepared by above-mentioned preparation method are by single A2B7Type phase composition.It should be noted
It is that La-Mg-Ni hydrogen bearing alloys involved in the present invention refer to the group for the alloy, wherein La, Mg and Ni being made up of La, Mg and Ni
Divide and be referred to prior art.For example, the chemical formula of La-Mg-Ni hydrogen bearing alloys is La2-xMgxNi7, wherein 0.2≤x≤0.5.
Meanwhile in above-mentioned preparation method, because the crystal grain of alloy after fast quenching is tiny, transition kinetics are very fast, can use
Shorter annealing time can obtain single A2B7The La-Mg-Ni hydrogen bearing alloys of phase.In addition, this method is easy to grasp, it is adapted to big
Large-scale production.
It should be noted that all know as those skilled in the art, A2B7Type is mutually (RE, Mg)2Ni7Phase, RE are represented
Rare earth element.Similarly, AB2、AB3、A5B19Type is respectively mutually (RE, Mg) Ni2, (RE, Mg) Ni3, (RE, Mg)5Ni19Phase, AB5Type phase
For RENi5Phase.
It is described in more detail below according to the exemplary of the preparation methods of La-Mg-Ni hydrogen bearing alloys provided by the invention
Embodiment.However, these illustrative embodiments can be implemented by many different forms, and it is not construed as
It is only limited to embodiments set forth herein.It should be appreciated that these embodiments are provided so that the public affairs of the application
Open thorough and complete, and the design of these illustrative embodiments is fully conveyed to those of ordinary skill in the art.
First, the mixed-metal feedstock prepared in proportion is subjected to melting, obtains liquid alloy.Wherein, a kind of preferred
Embodiment in, by mixed-metal feedstock carry out melting the step of include：0.01 is filled with to vacuum induction melting furnace~
0.1MPa inert gas；Mixed-metal feedstock is melted at a temperature of 1573K~1873K afterwards, and kept for 1~5 minute.
Now, the composition for obtaining liquid alloy is more uniform.
In order to further discharge the air in vacuum induction melting furnace, it is preferable that be filled with 0.01~0.1MPa inertia
The step of gas, includes：Vacuum induction melting furnace is evacuated to 1 × 10-4Below Pa, inert gas is filled with to normal pressure；Take out again
Vacuum is to 1 × 10-4Below Pa, and it is filled with 0.01~0.1MPa inert gas.
La, Mg and Ni simple metal are proportionally configured, and for Mg additions 5%-10% scaling loss amount, obtains hybrid metal
Raw material.
It should be noted that it is the gas of 'inertia' that inert gas herein, which can be the activity of production in this area, i.e.,
Refer to 18 race's elements on the periodic table of elements, such as helium etc..Vacuum induction melting furnace can use common model in this area
Stove.It is of course also possible to use other smelting furnaces carry out melting, such as mid-frequency melting furnace or high-frequency melting furnace etc., its specific work
Skill parameter is referred to prior art progress, as long as can be melted mixed-metal feedstock and obtain uniform liquid alloy.
Then, liquid alloy spray is fallen quickly to be cooled down on chill roll, obtains alloy after fast quenching, wherein chill roll
Linear resonance surface velocity is 3~8m/s.In the step, by the way that the linear resonance surface velocity of chill roll is defined into 3~8m/s, so as to incite somebody to action
AB in alloy after fast quenching5The content of type phase is controlled in appropriate scope (its volume content should be less than 20%), while obtains composition
With alloy after the fast quenching of even tissue.
Specifically, alloy includes AB after fast quenching2Type phase, AB3Type phase, A2B7Type phase and AB5Type phase, wherein AB5The body of type phase
Product content is less than 20%.It is further preferable that the linear resonance surface velocity of chill roll is 4~6m/s, AB5The volume content of type phase be 10~
15%.Those skilled in the art can be according to the teachings of the present invention, by controlling the linear resonance surface velocity of chill roll, to control AB5
The volume content of type phase.When the linear resonance surface velocity of chill roll is 3~8m/s, its universal law is：The surface linear speed of chill roll
Degree is bigger, obtains AB5The volume content of type phase is smaller.When the linear resonance surface velocity of chill roll is when outside 3~8m/s, obtained
AB5The volume content of type phase is significantly greater than 30%.
Alloy is strip after the step obtains fast quenching, and its thickness can be set according to actual process demand, such as
Thickness is 40~70 μm.In addition, the crystal grain that the step obtains alloy after fast quenching is smaller, it is preferable that the crystalline substance of alloy after fast quenching
Particle size is 2~10 μm.Now, because the crystal grain of alloy after fast quenching is tiny, transition kinetics are very fast, can use shorter move back
The fiery time can obtain single A2B7The La-Mg-Ni hydrogen bearing alloys of type phase.
In the step, chill roll can be copper roller, can also use other metal materials.Cooling medium can be water etc..
Specifically, the step can be：Liquid alloy is injected into tundish, is fallen using inert gas spray and is carried out quickly in water-cooled copper roller
Cooling, the linear resonance surface velocity of copper roller is 3~8m/s, obtains the strip between 40-70 μm of thickness.
Finally, alloy after fast quenching is heat-treated, included the step of heat treatment：Under the protection of inert gas, first exist
1~2 hour is incubated at 500~600 DEG C, then 1~2 hour is incubated at 700~800 DEG C, is finally incubated 2 at 800~900 DEG C
~6 hours.
In the step, at 500~600 DEG C 1~2 hour is incubated and enables to after fast quenching AB in alloy2Type is first to AB3
Type phase in version, at 700~800 DEG C 1~2 hour is incubated and enables to after fast quenching AB in alloy3And AB5Type mutually undergoes phase transition shape
Into A2B7Type phase, A can be made by 800~900 DEG C being incubated 2~6 hours2B7Type phase in version is completed, and ensures that composition is uniform.
In a preferred embodiment, the step includes：Alloy is placed in vacuum heat treatment furnace after fast quenching, is taken out first
Vacuum is to 1 × 10-4Hereinafter, inert gas is filled with, repeatedly gas washing 2-3 times.Using such a embodiment can further discharge by
Air in vacuum induction melting furnace.
According to another aspect of the present invention, present invention also offers a kind of La-Mg-Ni hydrogen bearing alloys, La-Mg-Ni storages
Hydrogen alloy above-mentioned preparation method provided by the present invention is made.The La-Mg-Ni hydrogen bearing alloys that the preparation method is obtained by
A2B7Type phase composition, and A2B7Type is mutually found to have higher discharge capability and excellent cyclical stability, therefore the preparation side
The La-Mg-Ni hydrogen bearing alloys that method is obtained have good cyclical stability.
La-Mg-Ni hydrogen bearing alloys refer to the alloy being made up of La, Mg and Ni, and wherein La, Mg and Ni component are referred to
Prior art.For example, the chemical formula of La-Mg-Ni hydrogen bearing alloys is La2-xMgxNi7, wherein 0.2≤x≤0.5.
According to another aspect of the invention, present invention also offers a kind of La-Mg-Ni hydrogen bearing alloys, La-Mg-Ni storages
Hydrogen alloy is by A2B7Type phase composition.Because the La-Mg-Ni hydrogen bearing alloys are by A2B7Type phase composition, and A2B7Type is mutually found to have
Higher discharge capability and excellent cyclical stability, thus the La-Mg-Ni hydrogen bearing alloys that are obtained of the preparation method have it is good
Good cyclical stability.
La-Mg-Ni hydrogen bearing alloys provided by the invention and preparation method thereof are further illustrated below in conjunction with embodiment.
Embodiment 1
The chemical formula for the La-Mg-Ni hydrogen bearing alloys that the present embodiment provides is La1.8Mg0.2Ni7, and show through XRD analysis,
La-Mg-Ni hydrogen bearing alloys are only by single A2B7Type phase composition.Its preparation method comprises the following steps：
(1) by raw material dispensing in proportion, mixed-metal feedstock is obtained；Vacuum induction melting furnace is evacuated to 1 × 10-4Pa
Hereinafter, argon gas is filled with to normal pressure, is then evacuated to 1 × 10 again-4Below Pa, it is filled with 0.01MPa high-purity helium protection；
Mixed-metal feedstock is melted at a temperature of 1573K~1873K, and kept for 1 minute, obtains liquid alloy.
(2) liquid alloy spray is fallen and quickly cooled down in water-cooled copper roller, the linear resonance surface velocity of copper roller is 5m/s, is obtained
Alloy after fast quenching between 70 μm of thickness；XRD analysis show that the crystallite dimension of alloy is less than 8 μm after gained fast quenching, gained fast quenching
Phase structure of alloy type includes AB afterwards2、AB3、A2B7And AB5Type phase, wherein AB5The content of type phase is 18.9%.
(3) alloy after fast quenching is placed in vacuum heat treatment furnace, is evacuated to 1 × 10 first-4Below Pa, argon gas is filled with,
Gas washing 3 times repeatedly；Annealing is as follows using stage heating and thermal insulation mode, detailed process：600 DEG C are heated to, is incubated 1 hour；Add
Heat is incubated 1 hour to 700 DEG C；800 DEG C are heated to, is incubated 6 hours.
Embodiment 2
The chemical formula for the La-Mg-Ni hydrogen bearing alloys that the present embodiment provides is La1.5Mg0.5Ni7, and show through XRD analysis,
La-Mg-Ni hydrogen bearing alloys are only by single A2B7Type phase composition.Its preparation method comprises the following steps：
(1) by raw material dispensing in proportion, mixed-metal feedstock is obtained；Vacuum induction melting furnace is evacuated to 1 × 10-4Pa
Hereinafter, argon gas is filled with to normal pressure, is then evacuated to 1 × 10 again-4Below Pa, it is filled with 0.1MPa high-purity helium protection；
Mixed-metal feedstock is melted at a temperature of 1573K~1873K, and kept for 1 minute, obtains liquid alloy.
(2) liquid alloy spray is fallen and quickly cooled down in water-cooled copper roller, the linear resonance surface velocity of copper roller is 5m/s, is obtained
Alloy after fast quenching between 70 μm of thickness；XRD analysis show that the crystallite dimension of alloy is less than 8 μm after gained fast quenching, gained fast quenching
Phase structure of alloy type includes AB afterwards2、AB3、A2B7And AB5Type phase, wherein AB5The content of type phase is 12.9%.
(3) alloy after fast quenching is placed in vacuum heat treatment furnace, is evacuated to 1 × 10 first-4Below Pa, argon gas is filled with,
Gas washing 2 times repeatedly；Annealing is as follows using stage heating and thermal insulation mode, detailed process：600 DEG C are heated to, is incubated 2 hours；Add
Heat is incubated 2 hours to 700 DEG C；900 DEG C are heated to, is incubated 4 hours.
Embodiment 3
The chemical formula for the La-Mg-Ni hydrogen bearing alloys that the present embodiment provides is La1.7Mg0.3Ni7, and show through XRD analysis,
La-Mg-Ni hydrogen bearing alloys are only by single A2B7Type phase composition.Its preparation method comprises the following steps：
(1) by raw material dispensing in proportion, mixed-metal feedstock is obtained；Vacuum induction melting furnace is evacuated to 1 × 10-4Pa
Hereinafter, argon gas is filled with to normal pressure, is then evacuated to 1 × 10 again-4Below Pa, it is filled with 0.1MPa high-purity helium protection；
Mixed-metal feedstock is melted at a temperature of 1573K~1873K, and kept for 1 minute, obtains liquid alloy.
(2) liquid alloy spray is fallen and quickly cooled down in water-cooled copper roller, the linear resonance surface velocity of copper roller is 5m/s, is obtained
Alloy after fast quenching between 70 μm of thickness；XRD analysis show that the crystallite dimension of alloy is less than 8 μm after gained fast quenching, gained fast quenching
Phase structure of alloy type includes AB afterwards2、AB3、A2B7And AB5Type phase, wherein AB5The content of type phase is 16.9%.
(3) alloy after fast quenching is placed in vacuum heat treatment furnace, is evacuated to 1 × 10 first-4Below Pa, argon gas is filled with,
Gas washing 2 times repeatedly；Annealing is as follows using stage heating and thermal insulation mode, detailed process：500 DEG C are heated to, is incubated 2 hours；Add
Heat is incubated 2 hours to 800 DEG C；850 DEG C are heated to, is incubated 6 hours.
Embodiment 4
The chemical formula for the La-Mg-Ni hydrogen bearing alloys that the present embodiment provides is La1.7Mg0.3Ni7, and show through XRD analysis,
La-Mg-Ni hydrogen bearing alloys are only by single A2B7Type phase composition.Its preparation method comprises the following steps：
(1) by raw material dispensing in proportion, mixed-metal feedstock is obtained；Vacuum induction melting furnace is evacuated to 1 × 10-4Pa
Hereinafter, argon gas is filled with to normal pressure, is then evacuated to 1 × 10 again-4Below Pa, it is filled with 0.1MPa high-purity helium protection；
Mixed-metal feedstock is melted at a temperature of 1573K~1873K, and kept for 1 minute, obtains liquid alloy.
(2) liquid alloy spray is fallen and quickly cooled down in water-cooled copper roller, the linear resonance surface velocity of copper roller is 3m/s, is obtained
Alloy after fast quenching between 70 μm of thickness；XRD analysis show that the crystallite dimension of alloy is less than 8 μm after gained fast quenching, gained fast quenching
Phase structure of alloy type includes AB afterwards2、AB3、A2B7And AB5Type phase, wherein AB5The content of type phase is 17.2%.
(3) alloy after fast quenching is placed in vacuum heat treatment furnace, is evacuated to 1 × 10 first-4Below Pa, argon gas is filled with,
Gas washing 2 times repeatedly；Annealing is as follows using stage heating and thermal insulation mode, detailed process：500 DEG C are heated to, is incubated 2 hours；Add
Heat is incubated 2 hours to 800 DEG C；850 DEG C are heated to, is incubated 2 hours.
Embodiment 5
The chemical formula for the La-Mg-Ni hydrogen bearing alloys that the present embodiment provides is La1.7Mg0.3Ni7, and show through XRD analysis,
La-Mg-Ni hydrogen bearing alloys are only by single A2B7Type phase composition.Its preparation method comprises the following steps：
(1) by raw material dispensing in proportion, mixed-metal feedstock is obtained；Vacuum induction melting furnace is evacuated to 1 × 10-4Pa
Hereinafter, argon gas is filled with to normal pressure, is then evacuated to 1 × 10 again-4Below Pa, it is filled with 0.1MPa high-purity helium protection；
Mixed-metal feedstock is melted at a temperature of 1573K~1873K, and kept for 1 minute, obtains liquid alloy.
(2) liquid alloy spray is fallen and quickly cooled down in water-cooled copper roller, the linear resonance surface velocity of copper roller is 8m/s, is obtained
Alloy after fast quenching between 0.7 μm of thickness；XRD analysis show that the crystallite dimension of alloy is less than 8 μm after gained fast quenching, and gained is fast
Phase structure of alloy type includes AB after quenching2、AB3、A2B7And AB5Type phase, wherein AB5The content of type phase is 14.3%.
(3) alloy after fast quenching is placed in vacuum heat treatment furnace, is evacuated to 1 × 10 first-4Below Pa, argon gas is filled with,
Gas washing 2 times repeatedly；Annealing is as follows using stage heating and thermal insulation mode, detailed process：600 DEG C are heated to, is incubated 2 hours；Add
Heat is incubated 2 hours to 700 DEG C；800 DEG C are heated to, is incubated 2 hours.
Comparative example 1
The chemical formula for the La-Mg-Ni hydrogen bearing alloys that this comparative example provides is La1.7Mg0.3Ni7, and show through XRD analysis,
La-Mg-Ni hydrogen bearing alloys are by AB3、AB5、A2B7Type phase composition.Its preparation method comprises the following steps：
(1) by raw material dispensing in proportion, mixed-metal feedstock is obtained；Vacuum induction melting furnace is evacuated to 1 × 10-4Pa
Hereinafter, argon gas is filled with to normal pressure, is then evacuated to 1 × 10 again-4Below Pa, it is filled with 0.1MPa high-purity helium protection；
Mixed-metal feedstock is melted at a temperature of 1573K~1873K, and kept for 1 minute, obtains liquid alloy.
(2) liquid alloy spray is fallen and quickly cooled down in water-cooled copper roller, the linear resonance surface velocity of copper roller is 2.6m/s, is obtained
Alloy after fast quenching between 80 μm of thickness；XRD analysis show that the crystallite dimension of alloy is more than 10 μm after gained fast quenching, gained
Phase structure of alloy type includes AB after fast quenching2、AB3、A2B7And AB5Type phase, wherein AB5The content of type phase is 30.3%.
(3) alloy after fast quenching is placed in vacuum heat treatment furnace, is evacuated to 1 × 10 first-4Below Pa, argon gas is filled with,
Gas washing 2 times repeatedly；Annealing is as follows using stage heating and thermal insulation mode, detailed process：500 DEG C are heated to, is incubated 2 hours；Add
Heat is incubated 2 hours to 800 DEG C；900 DEG C are heated to, is incubated 2 hours.
Comparative example 2
The chemical formula for the La-Mg-Ni hydrogen bearing alloys that this comparative example provides is La1.7Mg0.3Ni7, and show through XRD analysis,
La-Mg-Ni hydrogen bearing alloys are by AB3、AB5、A2B7Type phase composition.Its preparation method comprises the following steps：
(1) by raw material dispensing in proportion, mixed-metal feedstock is obtained；Vacuum induction melting furnace is evacuated to 1 × 10-4Pa
Hereinafter, argon gas is filled with to normal pressure, is then evacuated to 1 × 10 again-4Below Pa, it is filled with 0.1MPa high-purity helium protection；
Mixed-metal feedstock is melted at a temperature of 1573K~1873K, and kept for 1 minute, obtains liquid alloy.
(2) liquid alloy spray is fallen and quickly cooled down in water-cooled copper roller, the linear resonance surface velocity of copper roller is 8.8m/s, is obtained
Alloy after fast quenching between 70 μm of thickness；XRD analysis show that the crystallite dimension of alloy is less than 5 μm after gained fast quenching, and gained is fast
Phase structure of alloy type includes AB after quenching2、AB3、A2B7And AB5Type phase, wherein AB5The content of type phase is 27.3%.
(3) alloy after fast quenching is placed in vacuum heat treatment furnace, is evacuated to 1 × 10 first-4Below Pa, argon gas is filled with,
Gas washing 2 times repeatedly；Annealing is as follows using stage heating and thermal insulation mode, detailed process：500 DEG C are heated to, is incubated 2 hours；Add
Heat is incubated 2 hours to 800 DEG C；900 DEG C are heated to, is incubated 2 hours.
Comparative example 3
The chemical formula for the La-Mg-Ni hydrogen bearing alloys that the present embodiment provides is La1.7Mg0.3Ni7, and show through XRD analysis,
La-Mg-Ni hydrogen bearing alloys are by AB2、AB3、AB5And A2B7Type phase composition.Its preparation method comprises the following steps：
(1) by raw material dispensing in proportion, mixed-metal feedstock is obtained；Vacuum induction melting furnace is evacuated to 1 × 10-4Pa
Hereinafter, argon gas is filled with to normal pressure, is then evacuated to 1 × 10 again-4Below Pa, it is filled with 0.1MPa high-purity helium protection；
Mixed-metal feedstock is melted at a temperature of 1573K~1873K, and kept for 1 minute, obtains liquid alloy.
(2) liquid alloy spray is fallen and quickly cooled down in water-cooled copper roller, the linear resonance surface velocity of copper roller is 8m/s, is obtained
Alloy after fast quenching between 70 μm of thickness；XRD analysis show that the crystallite dimension of alloy is less than 8 μm after gained fast quenching, gained fast quenching
Phase structure of alloy type includes AB afterwards2、AB3、A2B7And AB5Type phase, wherein AB5The content of type phase is 27.3%.
(3) alloy after fast quenching is placed in vacuum heat treatment furnace, is evacuated to 1 × 10 first-4Below Pa, argon gas is filled with,
Gas washing 2 times repeatedly；Annealing process is as follows：820 DEG C are heated to, is incubated 6 hours.
Comparative example 4
The chemical formula for the La-Mg-Ni hydrogen bearing alloys that the present embodiment provides is La1.7Mg0.3Ni7, and show through XRD analysis,
La-Mg-Ni hydrogen bearing alloys are by AB5、A2B7And A5B19Type phase composition.Its preparation method comprises the following steps：
(1) by raw material dispensing in proportion, mixed-metal feedstock is obtained；Vacuum induction melting furnace is evacuated to 1 × 10-4Pa
Hereinafter, argon gas is filled with to normal pressure, is then evacuated to 1 × 10 again-4Below Pa, it is filled with 0.1MPa high-purity helium protection；
Mixed-metal feedstock is melted at a temperature of 1573K~1873K, and kept for 1 minute, obtains liquid alloy.
(2) liquid alloy spray is fallen and quickly cooled down in water-cooled copper roller, the linear resonance surface velocity of copper roller is 8m/s, is obtained
Alloy after fast quenching between 70 μm of thickness；XRD analysis show that the crystallite dimension of alloy is less than 8 μm after gained fast quenching, gained fast quenching
Phase structure of alloy type includes AB afterwards2、AB3、A2B7And AB5Type phase, wherein AB5The content of type phase is 27.3%.
(3) alloy after fast quenching is placed in vacuum heat treatment furnace, is evacuated to 1 × 10 first-4Below Pa, argon gas is filled with,
Gas washing 2 times repeatedly；Annealing is as follows using stage heating and thermal insulation mode, detailed process：480 DEG C are heated to, is incubated 2 hours；Add
Heat is incubated 2 hours to 670 DEG C；920 DEG C are heated to, is incubated 4 hours.
Test：Alloy and La-Mg-Ni hydrogen bearing alloys after the fast quenching that the present invention obtains to embodiment 1 to 5 and comparative example 1 to 5
Pattern test and XRD tests are carried out.In order to save length, the present invention only gives alloy after the fast quenching obtained to embodiment 1
Pattern test result and XRD test results have been carried out with La-Mg-Ni hydrogen bearing alloys.
Fig. 2 shows the metallographic structure of alloy after the fast quenching that embodiment 1 obtains, and shows to apply alloy after the fast quenching of the acquisition of example 1
It is smaller including 4 kinds of compound phases, crystal grain.Fig. 3 shows the XRD spectrum of alloy after the fast quenching that embodiment 1 obtains, and finds to implement
Alloy is by AB after the fast quenching that example 1 obtains2、AB3、AB5And A2B7Type phase composition.
Fig. 4 a show the metallographic structure for the La-Mg-Ni hydrogen bearing alloys that embodiment 1 obtains, and Fig. 4 b show that embodiment 1 obtains
The metallographic structure (backscattered electron image figure) of the La-Mg-Ni hydrogen bearing alloys obtained, Fig. 4 c show the La-Mg- that embodiment 1 obtains
The power spectrum Surface scan distribution of 3 kinds of elements in Ni hydrogen bearing alloys.Fig. 5 shows the La-Mg-Ni hydrogen bearing alloys that embodiment 1 obtains
XRD spectrum.From Fig. 4 a to 4c, the La-Mg-Ni hydrogen bearing alloys that embodiment 1 obtains are in homogeneous structure.As shown in Figure 5, implement
The La-Mg-Ni hydrogen bearing alloys that example 1 obtains are only by A2B7Type phase composition.
As can be seen from the above embodiments, the above-mentioned example of the present invention realizes following technique effect：During the present invention uses
Low speed quick-quenching method is by AB5The content of type phase suppresses in appropriate scope, while is closed after obtaining composition and the fast quenching of even tissue
Gold, then using stage annealing process, insulation is stopped respectively in low temperature to high temperature section, make the low melting point phase in alloy after fast quenching
Mutually undergone phase transition successively with high-melting-point, so as to obtain the A of single type2B7Type phase.Simultaneously as the crystal grain of alloy is thin after fast quenching
Small, transition kinetics are very fast, shorter annealing time can be used to obtain single A2B7The La-Mg-Ni hydrogen storages of type phase are closed
Gold.In addition, this method is easy to grasp, it is adapted to large-scale production.
The preferred embodiments of the present invention are these are only, are not intended to limit the invention, for those skilled in the art
For member, the present invention can have various modifications and variations.Any modification within the spirit and principles of the invention, being made,
Equivalent substitution, improvement etc., should be included in the scope of the protection.
Claims (5)
1. a kind of preparation method of La-Mg-Ni hydrogen bearing alloys, it is characterised in that the preparation method comprises the following steps：
The mixed-metal feedstock prepared in proportion is subjected to melting, obtains liquid alloy；
Liquid alloy spray is fallen and quickly cooled down on chill roll, obtains alloy after fast quenching, wherein the chill roll
Linear resonance surface velocity is 3~8m/s；Alloy includes AB after the fast quenching2Type phase, AB3Type phase, A2B7Type phase and AB5Type phase, wherein institute
State AB5The volume content of type phase is less than 20%；The thickness of alloy is 40~70 μm after the fast quenching, and crystallite dimension is 2~10 μm；
Alloy after the fast quenching is heat-treated, included the step of the heat treatment：Under the protection of inert gas, first exist
1~2 hour is incubated at 500~600 DEG C, then 1~2 hour is incubated at 700~800 DEG C, is finally incubated 2 at 800~900 DEG C
~6 hours；
The chemical formula of the La-Mg-Ni hydrogen bearing alloys is La2-xMgxNi7, wherein 0.2≤x≤0.5；The La-Mg-Ni hydrogen storages
Alloy is by single A2B7Type phase composition.
2. preparation method according to claim 1, it is characterised in that the step of mixed-metal feedstock is subjected to melting
Including：
0.01~0.1MPa the inert gas is filled with to vacuum induction melting furnace；
The mixed-metal feedstock is melted at a temperature of 1573K~1873K afterwards, and kept for 1~5 minute.
3. preparation method according to claim 2, it is characterised in that be filled with the 0.01~0.1MPa inert gas
Step includes：
The vacuum induction melting furnace is evacuated to 1 × 10-4Below Pa, the inert gas is filled with to normal pressure；
1 × 10 is evacuated to again-4Below Pa, and it is filled with the 0.01~0.1MPa inert gas.
4. preparation method according to claim 1, it is characterised in that in the step of the heat treatment, charged pressure is less than
The 0.1MPa inert gas.
5. a kind of La-Mg-Ni hydrogen bearing alloys, it is characterised in that the La-Mg-Ni hydrogen bearing alloys in Claims 1-4 by appointing
Preparation method described in one is made.
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