CN109848427A - A method of it improving palladium and coats zirconium base hydrogen-absorbing material antitoxinization cyclical stability - Google Patents
A method of it improving palladium and coats zirconium base hydrogen-absorbing material antitoxinization cyclical stability Download PDFInfo
- Publication number
- CN109848427A CN109848427A CN201811475669.0A CN201811475669A CN109848427A CN 109848427 A CN109848427 A CN 109848427A CN 201811475669 A CN201811475669 A CN 201811475669A CN 109848427 A CN109848427 A CN 109848427A
- Authority
- CN
- China
- Prior art keywords
- hydrogen
- absorbing material
- palladium
- zirconium
- alloy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Powder Metallurgy (AREA)
Abstract
The invention discloses a kind of methods of raising palladium cladding zirconium-based metallic hydrogen-absorbing material antitoxinization cyclical stability.Specific steps are as follows: circulation suction hydrogen release is carried out to zirconium-base alloy hydrogen-absorbing material first and obtains the shaggy metallic particles of fine uniform for several times, one layer of Pd film is coated in surface of metal particles using the method for chemical plating, then the heat treatment of certain time is carried out to the metallic particles after cladding, make the zirconium in palladium film and alloy substrate that partial miscibility occur, to enhance membranous layer binding force.The antitoxinization metal hydrogen-absorbing material prepared by this method is containing CO, O2、N2Etc. still can quickly inhale hydrogen release in the hydrogen of foreign gases, and the further dusting degree of alloying pellet is smaller in cyclic process, palladium film is not easily to fall off, ensure that the stability of material hydrogen storage property in the hydrogen isotope gas of impure gas, i.e. material has longer service life cycle.
Description
Technical field
The invention belongs to hydrogen isotope recycling, storage material technical field, are related to a kind of raising palladium cladding zirconium base suction hydrogen material
Expect the method for antitoxinization cyclical stability, and in particular to a kind of that there is long circulating in the hydrogen isotope gas containing foreign gas
The preparation method of the palladium cladding zirconium-based metallic hydrogen-absorbing material of service life.
Background technique
Hydrogen and its isotope important role in the energy especially nuclear energy field, metal hydrogen-absorbing material may be implemented pair
The controlled absorbed and release of hydrogen and its isotope meet the safe storage of hydrogen and transport demand.But in actual application, hydrogen
Often contain partial impurities gas in isotope gas, such as CO, CO2、CH4、O2、N2Deng.These foreign gases often be easier with
Hydrogen-absorbing material reacts, and the film layer of fine and close metal carbides, nitride, oxide is formed on the surface of the material, to stop
Hydrogen is substantially reduced hydrogen-absorbing material hydrogen-absorbing ability to spreading inside alloy, or even completely loses, i.e., impurity gas occurs for material
Body poisoning.Therefore, need it is poisoning to the anti-foreign gas of hydrogen-absorbing material can be carried out improvement, to meet hydrogen-absorbing material containing miscellaneous
Efficient suction hydrogen in matter hydrogen isotope gas.
Currently, element doping, surface be modified and the methods of redox be used to improve metal hydrogen-absorbing material resist it is poisoning
Energy.Wherein the most effective means are that surface coating is modified, and such as coating on hydrogen-absorbing material surface there is selectivity to penetrate hydrogen
Metal or alloy film of ability etc..Metal Pd film has excellent selective penetrated property, for most of in hydrogen isotope gas
Foreign gas O2、CO、CO2、CH4It is at present more Deng having preferable anti-poisoning capability, and hydrogen transmitance with higher
Common method.But dusting, while useization easily in practical applications, occurs during circulation inhales hydrogen release due to hydrogen-absorbing material
The palladium film membranous layer binding force for learning plating cladding is relatively poor, to be easy to happen film layer cracking in use and fall off, in turn
Alloy is caused to be poisoned.
Summary of the invention
To solve the problems existing in the above prior art, it is an object of the invention to propose a kind of raising palladium cladding zirconium base
The method of hydrogen-absorbing material antitoxinization cyclical stability.Using the palladium cladding zirconium-based metallic hydrogen-absorbing material of this method preparation impure
Have in the hydrogen isotope gas of gas compared with long circulating service life, can avoid that film layer cracking occurs in use and takes off
It falls, and then realizes and containing CO, CO2、CH4、O2、N2Etc. be recycled for multiple times in the hydrogen isotope gas of foreign gases and inhale hydrogen appearance
Amount and suction hydrogen dynamics are without significant decaying.
To achieve the above object, the invention adopts the following technical scheme:
A method of it improving palladium and coats zirconium-based metallic hydrogen-absorbing material antitoxinization cyclical stability, comprising the following steps:
1) it prepares zirconium-base alloy: using vacuum high-frequency induction melting, turning over melting 3 times, and pass through situ heat treatment 5min
Alloy cast ingot is prepared, Mechanical Crushing is at bulk；
2) palladium cladding is prepared with alloyed powder: under the conditions of certain temperature and Hydrogen Vapor Pressure, putting the suction of metal hydrogen-absorbing material
Hydrogen recurring number time dusting, obtains surface microscopic topographic in the alloyed powder of coarse irregular status with spare；
3) chemical plating: the appropriate alloyed powder inhaled after hydrogen release circulation is taken, pours into reaction kettle, successively carries out fluorination and chemical plating
Palladium processing；
4) it is heat-treated: the alloyed powder for coating Pd film being encapsulated in quartz ampoule, and argon filling gas shielded, quartz ampoule is put into heat
In treatment furnace, 500 DEG C are warming up to the rate of 10 DEG C/min, keeps the temperature that cool to room temperature after 8h with the furnace spare, make palladium film and alloy
Partial miscibility occurs for the zirconium in matrix, enhances membranous layer binding force, obtains palladium cladding zirconium-based metallic hydrogen-absorbing material.
Antitoxinization performance test: the sample after heat treatment is inhaled into hydrogen in 25 DEG C, 0.6MPa, 400 DEG C vacuumize dehydrogenation 1h's
30 circulate operations are carried out under test condition, record data.
Wherein, the circulation inhales the method for hydrogen release are as follows: under the conditions of certain temperature and Hydrogen Vapor Pressure, metal is made to inhale hydrogen material
Material inhales hydrogen release recurring number time dusting, i.e., is depressed with the alloying pellet being mechanically pulverized in room temperature 0.5~2MPa hydrogen and inhale hydrogen saturation,
400 DEG C of dehydrogenation 1h are recycled 3~10 times.
Wherein, the metal hydrogen-absorbing material inhales the partial size after hydrogen release recycles less than 100 μm.
Wherein, in the plating solution of the chemical plating Pd film, PdCl2Concentration be 3~5g/L, plating temperature be 50~60 DEG C,
Single batch alloy amount is 0.5~10kg/L, and the rate of addition of reducing agent is 2~500mL/min, 10~30min of plating time.
Wherein, the heat treatment temperature is 400~800 DEG C, and heat treatment time is 2~12 hours, and heat-treating atmosphere is height
Pure hydrogen, high-purity argon gas or high-purity helium.
Beneficial effects of the present invention:
1, the present invention obtains initial grain using the method for inhaling hydrogen release circulation before to zirconium-based metallic hydrogen-absorbing material chemical palladium-plating
Alloyed powder of the diameter less than 100 μm advantageously reduces the further dusting of alloying pellet in use, to inhibit antitoxinization
Hydrogen-absorbing material the cracking of film layer and falls off in cyclic process.Meanwhile the alloying pellet by inhaling hydrogen release circulation is with higher
Surface roughness and biggish specific surface area, are conducive to the raising of membranous layer binding force.
2, the present invention makes zirconium alloy substrates and palladium film that counterdiffusion occur using heat-treating methods after electroless plating, thus
The solution area for forming Pd and Zr greatly improves membranous layer binding force, and the metal hydrogen-absorbing material after realizing cladding is in the hydrogen containing impurity
Hydrogen release recycling can be repeatedly inhaled in isotope atmosphere, extend hydrogen storage isotope materials'use duration.
3, using the more mechanical powder of service life cycle of the antitoxinization hydrogen-absorbing material of the Pd film cladding of the method for the present invention preparation
The alloy of plating palladium significantly improves after broken, and in inhaling hydrogen release cyclic process, absorption hydrogen capacity and suction hydrogen dynamics decaying are smaller, greatly
It is big to improve materials'use efficiency.
4, the method for the present invention is adaptable to a variety of zirconium-base alloys, such as Zr-Co system, Zr-Fe system, and easy to operate is easy to real
Existing, material antitoxinization cyclical stability is promoted significant.
Detailed description of the invention
Fig. 1 is that ZrTiNiCo alloy hydrogen absorption and desorption of the present invention recycles 5 rear surface microscopic appearances
Fig. 2 is that ZrTiNiCo alloy surface of the present invention coats Pd film pattern.
Fig. 3 is ZrTiNiCo alloy surface cladding Pd film pattern after present invention heat treatment.
The palladium film cladding ZrTiNiCo alloy of Fig. 4 present aspect preparation and the antitoxinization ZrTiNiCo alloy of conventional method preparation
The comparison of hydrogen release cycle life is inhaled in impure gas hydrogen.
ZrTiNiCo alloy surface coats Pd film pattern after Fig. 5 is mechanically pulverized.
The ZrTiNiCo hydrogen-absorbing material of Fig. 6 present aspect preparation the 30th suction hydrogen dynamics in the hydrogen of impure gas is bent
Line chart.
Specific embodiment
The present invention is described in more detail with reference to the accompanying drawings and examples.
Embodiment 1
ZrTiNiCo alloy is prepared using vacuum high-frequency induction melting, Mechanical Crushing is less than the bulk of 20mm at diameter.So
Alloy block is placed in Sievert testboard sample jar afterwards, is evacuated to 10-2Pa is hereinafter, be warming up to 400 after room temperature calibration volume
DEG C, continue to vacuumize system 1 hour, be then cooled to 25 DEG C, is depressed in initial 2MPa hydrogen and inhale hydrogen to being saturated, be warming up to again
400 DEG C and 1h is vacuumized, so inhales hydrogen release and recycle 5 times, sample jar is cooled to room temperature, the alloyed powder taken out after inhaling hydrogen dusting is standby
With.Alloyed powder surface microscopic topographic after circulation suction hydrogen release is in coarse irregular status, as shown in Figure 1.
It takes 100g to inhale the ZrTiNiCo alloyed powder after hydrogen release circulation, pours into reaction kettle, successively carry out fluorination and chemical plating
Palladium is handled, and mechanical stirring is kept in treatment process to ensure that alloying pellet is in suspended state and stirring without dead angle.Wherein it is fluorinated
Liquid composition are as follows: 1ml/L-HF, 1g/L-KF；Plating solution composition are as follows: 4.0g/L-PdCl2, 40g/L-EDTA-2Na, 40g/L-NH4Cl,
NH3H2O.Before chemical plating, plating solution is first warming up to 60 DEG C and adds alloyed powder, the reducing agent N for being 9% by concentration2N4·H2O solution
It is instilled in plating solution with the rate of 5mL/min and carries out chemical plating, stopped instilling reducing agent after 15min, coating process is completed, by alloy
Powder takes out from plating solution, and is cleaned 3 times with deionized water, then filters, and obtains the alloyed powder of Pd film cladding, and Fig. 2 is
ZrTiNiCo alloy surface coats the pattern photo of Pd film, cladding dense uniform of the Pd film in alloy surface.
The alloyed powder for coating Pd film is encapsulated in quartz ampoule, and argon filling gas shielded, quartz ampoule is put into heat-treatment furnace,
500 DEG C are warming up to the rate of 10 DEG C/min, cools to taking-up progress antitoxinization performance test after room temperature with the furnace after keeping the temperature 8h.
Hydrogen release loop test is inhaled in 1%O2+ 4%N2+ 5%He+90%H2Atmosphere in carry out, circulation inhale hydrogen release test-strips
Part are as follows: 25 DEG C, 0.6MPa suction hydrogen, 400 DEG C vacuumize dehydrogenation 1h, and hydrogen absorption capacity is shown in Fig. 4 with the variation relation of cycle-index.
Comparative example 1
ZrTiNiCo alloy, alloy of the Mechanical Crushing at partial size less than 100 μm are prepared using vacuum high-frequency induction melting
Grain is spare, using the alloying pellet of Mechanical Crushing as shown in figure 5, particle surface uniform ground.
The ZrTiNiCo alloyed powder for taking 100g Mechanical Crushing, is poured into reaction kettle, is successively carried out at fluorination and chemical palladium-plating
It manages, mechanical stirring is kept in treatment process to ensure that alloying pellet is in suspended state and stirring without dead angle.Wherein it is fluorinated liquid group
Become: 1ml/L-HF, 1g/L-KF；Plating solution composition are as follows: 4.0g/L-PdCl2, 40g/L-EDTA-2Na, 40g/L-NH4Cl,
NH3H2O.Before chemical plating, plating solution is first warming up to 60 DEG C and adds alloyed powder, the reducing agent N for being 9% by concentration2N4·H2O solution
It is instilled in plating solution with the rate of 5mL/min and carries out chemical plating, stopped instilling reducing agent after 15min, coating process is completed, by alloy
Powder takes out from plating solution, and is cleaned 3 times with deionized water, then filters, and obtains the alloyed powder of Pd film cladding, vacuum drying treatment
It takes out afterwards and carries out antitoxinization performance test.
Hydrogen release loop test is inhaled in 1%O2+ 4%N2+ 5%He+90%H2Atmosphere in carry out, circulation inhale hydrogen release test-strips
Part are as follows: 25 DEG C, 0.6MPa suction hydrogen, 400 DEG C vacuumize dehydrogenation 1h, and material hydrogen absorption capacity is shown in Fig. 4 with the variation relation of cycle-index
(black triangle).
As embodiment 1 and comparative example 1 it is found that using the absorption hydrogen capacity of the cladding of Pd film made from conventional method with following
The increase of ring number is remarkably decreased, and in the 30th circulation, hydrogen absorption capacity drops to 1.484wt.%, has dropped 25.1%.And
The application is by inhaling the dusting of hydrogen release circulation, palladium film cladding and the alloy of heat treatment, in inhaling hydrogen release cyclic process, hydrogen absorption capacity
Decaying is slow, and gradually stable in 1.88wt% or so, and the 30th hydrogen absorption capacity only has dropped not compared with first time hydrogen absorption capacity
To 5%, wherein the 30th Dynamic isotherms of hydrogen absorption in impure gas hydrogen as shown in fig. 6, after 30 circulations alloy
Still keep preferable dynamics.By comparison it is found that coating following for antitoxinization hydrogen-absorbing material using Pd film prepared by the method for the present invention
Ring service life is significantly improved compared with the alloy for plating palladium after mechanical crushing, and absorption hydrogen capacity and suction hydrogen dynamics decaying are smaller.
Technical solution of the present invention is described in detail in above-described embodiment.It is apparent that the present invention is not limited being retouched
The embodiment stated.Based on the embodiments of the present invention, those skilled in the art can also make a variety of variations accordingly, but appoint
What is equal with the present invention or similar variation shall fall within the protection scope of the present invention.
Claims (9)
1. it is a kind of improve palladium cladding zirconium-based metallic hydrogen-absorbing material antitoxinization cyclical stability method, which is characterized in that including with
Lower step:
1) it prepares zirconium-base alloy: alloy cast ingot being prepared using vacuum high-frequency induction melting, by its Mechanical Crushing at bulk；
2) palladium cladding is prepared with alloyed powder: the circulation of bulk alloy obtained by step 1) being inhaled hydrogen release dusting for several times, obtains surface microscopic
Pattern is spare in the alloyed powder of coarse irregular status；
3) chemical plating: taking alloyed powder obtained by step 2), pour into reaction kettle, successively carries out fluorination and chemical palladium-plating processing, obtains
Coat the alloyed powder of Pd film；
4) it is heat-treated: the alloyed powder of cladding Pd film obtained by step 3) being encapsulated in quartz ampoule, hot place is carried out in heat-treatment furnace
Reason obtains palladium cladding zirconium-based metallic hydrogen-absorbing material.
2. the method according to claim 1, wherein zirconium-base alloy described in step 1) is Zr-Co or Zr-Fe system
Alloy.
3. the method according to claim 1, wherein circulation described in step 2) inhales the concrete operations of hydrogen release are as follows:
Bulk alloy obtained by step 1) is placed in Sievert testboard sample jar, is evacuated to 10-2Pa is hereinafter, room temperature calibration volume
After be warming up to 400 DEG C of dehydrogenation 1h, continue to vacuumize system 1 hour, be then cooled to 25 DEG C, initial 2MPa hydrogen depress inhale hydrogen
To saturation, it is warming up to 400 DEG C again and vacuumizes 1h, so inhales hydrogen release and recycle 3~10 times, sample jar is cooled to room temperature.
4. the method according to claim 1, wherein after the circulation of metal hydrogen-absorbing material described in step 2) inhales hydrogen release
Partial size less than 100 μm.
5. the method according to claim 1, wherein in the plating solution of chemical plating Pd described in step 3), PdCl2's
Concentration is 3~5g/L, and plating temperature is 50~60 DEG C, and single batch alloyed powder amount is 0.5~10kg/L, the rate of addition of reducing agent
For 2~500mL/min, 10~30min of plating time, the reducing agent is N2N4·H2O solution.
6. the method according to claim 1, wherein the step 4) heat treatment temperature be 400~800 DEG C, heat
Handling the time is 2~12 hours, and heat-treating atmosphere is high-purity hydrogen, high-purity argon gas or high-purity helium.
7. turn over melting 3 times the method according to claim 1, wherein melting described in step 1), and
Alloy cast ingot is prepared by situ heat treatment 5min.
8. the method according to claim 1, wherein bulk alloy diameter described in step 1) is less than 20mm.
9. the method according to claim 1, wherein resisting for gained palladium cladding zirconium-based metallic hydrogen-absorbing material
Poison performance test, the sample after heat treatment is inhaled into hydrogen at room temperature, 300 DEG C or more dehydrogenations carry out antitoxinization loop test, note
Record data.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811475669.0A CN109848427A (en) | 2018-12-04 | 2018-12-04 | A method of it improving palladium and coats zirconium base hydrogen-absorbing material antitoxinization cyclical stability |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811475669.0A CN109848427A (en) | 2018-12-04 | 2018-12-04 | A method of it improving palladium and coats zirconium base hydrogen-absorbing material antitoxinization cyclical stability |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109848427A true CN109848427A (en) | 2019-06-07 |
Family
ID=66890664
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811475669.0A Pending CN109848427A (en) | 2018-12-04 | 2018-12-04 | A method of it improving palladium and coats zirconium base hydrogen-absorbing material antitoxinization cyclical stability |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109848427A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110777369A (en) * | 2019-11-10 | 2020-02-11 | 中电国基南方集团有限公司 | Active packaging hydrogen absorption material and preparation method thereof |
| CN111519051A (en) * | 2020-04-21 | 2020-08-11 | 上海申核能源工程技术有限公司 | Process for preparing hydrogen absorption material after nuclear facility accident |
| CN111540484A (en) * | 2020-04-21 | 2020-08-14 | 上海申核能源工程技术有限公司 | Hydrogen absorption material used under nuclear facility accident environmental condition |
| CN114408858A (en) * | 2022-01-05 | 2022-04-29 | 北京科技大学 | Preparation method of zirconium-based composite material capable of absorbing hydrogen at room temperature |
| CN115228235A (en) * | 2022-05-12 | 2022-10-25 | 有研工程技术研究院有限公司 | Hydrogen-helium gas separation device |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101067201A (en) * | 2007-06-12 | 2007-11-07 | 江苏大学 | Method for promoting preprocessing of copper-clad zirconium tungstate composite powder |
| CN101531532A (en) * | 2009-04-17 | 2009-09-16 | 上海应用技术学院 | Method for coating nickel-phosphorus cladding on surface of ZrO2 ceramic powder |
| CN103055795A (en) * | 2013-01-15 | 2013-04-24 | 北京联创宏业真空科技有限公司 | Getter and preparation method thereof |
| CN103668133A (en) * | 2013-09-09 | 2014-03-26 | 西北工业大学 | Method for Zr-based hydrogen storage alloy deposition of Pd film and plating solution for chemical plating |
| CN108160989A (en) * | 2016-12-07 | 2018-06-15 | 北京有色金属研究总院 | A kind of preparation method of antitoxinization metal hydrogen-absorbing material |
| US20180312951A1 (en) * | 2014-05-26 | 2018-11-01 | Hrl Laboratories, Llc | Hydride-coated microparticles and methods for making the same |
-
2018
- 2018-12-04 CN CN201811475669.0A patent/CN109848427A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101067201A (en) * | 2007-06-12 | 2007-11-07 | 江苏大学 | Method for promoting preprocessing of copper-clad zirconium tungstate composite powder |
| CN101531532A (en) * | 2009-04-17 | 2009-09-16 | 上海应用技术学院 | Method for coating nickel-phosphorus cladding on surface of ZrO2 ceramic powder |
| CN103055795A (en) * | 2013-01-15 | 2013-04-24 | 北京联创宏业真空科技有限公司 | Getter and preparation method thereof |
| CN103668133A (en) * | 2013-09-09 | 2014-03-26 | 西北工业大学 | Method for Zr-based hydrogen storage alloy deposition of Pd film and plating solution for chemical plating |
| US20180312951A1 (en) * | 2014-05-26 | 2018-11-01 | Hrl Laboratories, Llc | Hydride-coated microparticles and methods for making the same |
| CN108160989A (en) * | 2016-12-07 | 2018-06-15 | 北京有色金属研究总院 | A kind of preparation method of antitoxinization metal hydrogen-absorbing material |
Non-Patent Citations (1)
| Title |
|---|
| ZHANG, MI等: "Hydrogenation properties of Pd-coated Zr-based Laves phase compounds", 《VACUUM 》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110777369A (en) * | 2019-11-10 | 2020-02-11 | 中电国基南方集团有限公司 | Active packaging hydrogen absorption material and preparation method thereof |
| CN111519051A (en) * | 2020-04-21 | 2020-08-11 | 上海申核能源工程技术有限公司 | Process for preparing hydrogen absorption material after nuclear facility accident |
| CN111540484A (en) * | 2020-04-21 | 2020-08-14 | 上海申核能源工程技术有限公司 | Hydrogen absorption material used under nuclear facility accident environmental condition |
| CN114408858A (en) * | 2022-01-05 | 2022-04-29 | 北京科技大学 | Preparation method of zirconium-based composite material capable of absorbing hydrogen at room temperature |
| CN115228235A (en) * | 2022-05-12 | 2022-10-25 | 有研工程技术研究院有限公司 | Hydrogen-helium gas separation device |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109848427A (en) | A method of it improving palladium and coats zirconium base hydrogen-absorbing material antitoxinization cyclical stability | |
| US4312669A (en) | Non-evaporable ternary gettering alloy and method of use for the sorption of water, water vapor and other gases | |
| CN106898762B (en) | A kind of preparation method of lithium ion battery high-capacity cathode material | |
| CN108411182B (en) | Zr-Ti-Cr-V complex phase hydrogen storage alloy and preparation method thereof | |
| WO2020248644A1 (en) | Metal material and modification method of in situ dissolution on surface therefor | |
| CN105568110B (en) | It is a kind of to be used to store AB type hydrogen storage alloys of tritium and preparation method thereof | |
| CN104593651A (en) | Mg-Ti-RE-Ni-based hydrogen-storage alloy and preparation method thereof | |
| CN110224122A (en) | The preparation method of prelithiation alloy with porous structure | |
| CN105779848A (en) | Ferrotitanium-based hydrogen storage alloy | |
| CN103801252A (en) | Degassing agent with protective layer as well as preparation method thereof | |
| Hara et al. | Hydrogen absorption by Pd-coated ZrNi prepared by using Barrel-Sputtering System | |
| Ren et al. | Improved tolerance of Pd/Cu-treated metal hydride alloys towards air impurities | |
| WO1990015415A1 (en) | Improvements in materials | |
| CN112226663B (en) | High-circulation-capacity ZrCo-based hydrogen isotope storage alloy and preparation and application thereof | |
| CN109175349A (en) | Double rare earth solid solution base hydrogen storage materials of a kind of high-performance and preparation method thereof | |
| CN107299269B (en) | A kind of W-Cr-Al composite material and preparation method of resistance to high temperature oxidation | |
| CN103789573B (en) | A kind of Zr base Laves phase hydrogen storage alloy and preparation method thereof | |
| CN102240812B (en) | Preparation method for uranium molybdenum alloy powder | |
| CN112174196B (en) | TiN/C coated lithium titanate tritium proliferation agent, preparation method and preparation device system thereof | |
| CN114293086B (en) | Hydrogen storage high-entropy alloy and preparation method thereof | |
| CN112071444B (en) | Uranium dioxide monocrystal/nano diamond composite fuel and preparation method thereof | |
| CN104259452A (en) | Method for enhancing air poison resistance of Zr2Fe alloy | |
| CN112102968B (en) | High-thermal-conductivity fuel core block and preparation method thereof | |
| CN103627945A (en) | Non-stoichiometric Zr-based AB2 type hydrogen storage alloy and preparation method thereof | |
| CN107758611A (en) | A kind of magnesium-base nanometer composite hydrogen-storing material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190607 |