CN108515187A - A kind of zirconium and the method for zircaloy hydrogenation process optimization - Google Patents
A kind of zirconium and the method for zircaloy hydrogenation process optimization Download PDFInfo
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- CN108515187A CN108515187A CN201810476189.XA CN201810476189A CN108515187A CN 108515187 A CN108515187 A CN 108515187A CN 201810476189 A CN201810476189 A CN 201810476189A CN 108515187 A CN108515187 A CN 108515187A
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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
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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
- B22F9/023—Hydrogen absorption
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Abstract
The method of zirconium and zircaloy hydrogenation process optimization of the present invention, processing step are as follows successively：(1) zirconium or zircaloy are placed in vacuum sintering furnace by vacuum activating, control vacuum degree≤1.0 × 10 in stove‑2It heats up after Pa, 30~90min is kept the temperature when in-furnace temperature rises to 150~350 DEG C, vacuum degree≤1.0 × 10 in stove are kept in heating and insulating process‑2Pa；(2) it hydrogenates, after vacuum activating, high-purity hydrogen is passed through into vacuum sintering furnace and carries out hydrogenation treatment, purity >=99.999% of the hydrogen.Vacuum activating step in this method can not only destroy the dense oxidation film of zirconium or Zr alloy surface, the osmotic resistance of hydrogen in hydrogenation process is set to reduce, hydrogen point is inhaled to shift to an earlier date, to reduce the hydrogenation temperature of zirconium or zircaloy, shorten hydrogenation soaking time, so that the hydrogen content of zircoium hydride is greatly improved and close to theoretical value, and oxygen content is made to be effectively controlled.
Description
Technical field
The invention belongs to zirconium and Zirconium alloy material fields, the more particularly to hydrogenation process of zirconium and zircaloy.
Background technology
Zirconium has excellent corrosion resistance, lower neutron absorption cross-section product, high molten as a kind of rare metal
The excellent properties such as boiling point, thus it is widely used in the fields such as military project, aerospace, nuclear reaction.HDH method is to prepare at present
Zirconium powder and the widest method of zircaloy powder, main includes hydrogenation, broken and three step of dehydrogenation, has simple for process, production cost
It is low, be easy to the advantages that large-scale production, wherein hydrogenation process is a pass in high quality zirconium powder and zircaloy powder preparation process
Key step, hydrogenation temperature and hydrogenation soaking time have great influence to the performance of the zircoium hydride of preparation.Due to hydrogenation and dehydrogenization
Method itself does not have the function of purification, and zirconium and Zr alloy surface easily adsorb hydrone and oxygen nitrogen in air etc., thus general
Logical hydrogen technique of inhaling will make zircoium hydride (ZrH obtained2) in oxygen content it is higher, hydrogen-sucking amount is insufficient and it is long to inhale the hydrogen process time, inhales hydrogen
Temperature is high, limits the application of HDH method and further development.
In order to optimize hydrogenation process, HDH method is promoted further to develop, the optimization of hydrogenation process and technological parameter
The great attention for all receiving researcher all the time and extensively research are chosen, and achieves a series of achievements in research, example
Such as, sponge zirconium oozes to hydrogen content is made after hydrogen 1h is 1.98wt.% at 700 DEG C, zircoium hydride that oxygen content is 0.46wt.% (see
Health builds rigid hydrogenation-dehydrogenations method and prepares zirconium powder and its performance characterization [J] Materials Science and Engineering of Powder Metallurgies .2015,20 (04):
655-660.), although the zircoium hydride hydrogen content that the technique obtains can meet follow-up destruction step, also have from hydrogen content theoretical value
Gap and hydrogenation temperature is higher, hydrogenation soaking time is longer and product oxygen content is higher；Application No. is CN201410606369.7
Patent in, hydrogenation process is carried out in the case where hydrogenation temperature is 800 DEG C nearly, 1~3h of heat preservation, hydrogen press nearly 200KPa, the hydrogenation process
The oxygen content of zircoium hydride is not only caused to increase, and hydrogenation temperature is high, hydrogenation soaking time is long, to actually preparing environment, equipment item
Part requires high.
Invention content
It is an object of the invention to overcome the deficiencies of the prior art and provide the sides that a kind of zirconium and zircaloy hydrogenation process optimize
Method to improve the hydrogen content of product zircoium hydride under lower hydrogenation temperature and hydrogenation pressure, to reduce its oxygen content, and shortens
Process time and reduction production cost.
The method of zirconium and zircaloy hydrogenation process optimization of the present invention is to increase vacuum before zirconium or zircaloy hydrogenation to live
Change step, processing step is as follows successively：
(1) vacuum activating
Zirconium or zircaloy are placed in vacuum sintering furnace, vacuum degree≤1.0 × 10 in stove are controlled-2It heats up after Pa, when in stove
Temperature keeps the temperature 30~90min when rising to 150~350 DEG C, vacuum degree≤1.0 × 10 in stove are kept in heating and insulating process- 2Pa；
(2) it hydrogenates
After vacuum activating, it is passed through high-purity hydrogen into vacuum sintering furnace and carries out hydrogenation treatment, the purity of the hydrogen >=
99.999%.
Above-mentioned zirconium and the method for zircaloy hydrogenation process optimization, step (2) the hydrotreated operation are：When gas in stove
Pressure heats up after reaching 120~180KPa, when in-furnace temperature rises to 450~650 DEG C, keeps the temperature 10~30min, is unloaded after heat preservation
Press and cool to the furnace room temperature, obtain hydrogenation zirconia material, kept in stove in heating and insulating process air pressure be 120~
180KPa,.
Above-mentioned zirconium and the method for zircaloy hydrogenation process optimization, the form of the zirconium is sponge zirconium, and the form of zircaloy is
Zirconium alloy pipe, zirconium alloy bar, airconium alloy plates or zircaloy bits.
Above-mentioned zirconium and the method for zircaloy hydrogenation process optimization, heating rate when heating up in vacuum activating step is to hydrogen
Change step technological parameter have no significant effect, in step of hydrogenation heat up when heating rate to hydrogenate zirconia material hydrogen content and
Oxygen content has no significant effect, and heating rate is mainly determined according to the vacuum sintering furnace of actual use.
Compared with prior art, the invention has the advantages that：
1, the present invention provides the new method that a kind of zirconium and zircaloy hydrogenation process optimize, the vacuum activating step in this method
The rapid dense oxidation film that can not only destroy zirconium or Zr alloy surface, makes the osmotic resistance of hydrogen in hydrogenation process reduce, and inhales hydrogen point
In advance, to reduce the hydrogenation temperature of zirconium or zircaloy, shorten hydrogenation soaking time, avoid point of zircoium hydride in hydrogenation process
Solution makes the hydrogen content of product zircoium hydride greatly improve and close to theoretical value, and can remove zirconium or the water of Zr alloy surface absorption
Molecule and hydroxyl etc., avoid them from reacting with zirconium in hydrogenation process, and oxygen content is made to be effectively controlled.
2, it is carried out in lower temperature and hydrogen pressure due to hydrogenation process provided by the present invention, thus reduces hydrogenation work
The danger of skill reduces the loss to equipment.
3, since the temperature of vacuum activating in the method for the invention is 150~350 DEG C, soaking time is 30~90min,
The temperature of hydrogenation is 450~650 DEG C, and soaking time is 10~30min, thus can reduce energy consumption and the requirement to equipment, is shortened
Process time reduces production cost, is conducive to industrialized production.
Description of the drawings
Fig. 1 is the stereoscan photograph of raw material sponge zirconium and the product after each step process in embodiment 2, wherein figure a
For the stereoscan photograph of raw material sponge zirconium, figure b is the sponge zirconium stereoscan photograph after vacuum activating, and figure c is institute after hydrogenation
Obtain the stereoscan photograph of zircoium hydride.
Fig. 2 is the infrared diffusing reflection spectrum of sponge zirconium block surface of vacuum activating before and after the processing in embodiment 1 and embodiment 2
Figure, wherein spectrogram 1 is the infrared spectrogram that diffuses of raw material sponge zirconium, and spectrogram 2 is the sponge through vacuum activating in embodiment 1
The infrared spectrogram that diffuses of zirconium, spectrogram 3 are the infrared spectrogram that diffuses of the sponge zirconium through vacuum activating in embodiment 2.
Specific implementation mode
It is described further below by the method that embodiment optimizes zirconium of the present invention and zircaloy hydrogenation process.
In following embodiment, gained zircoium hydride has carried out H, O content measures, and the equipment used is TCH-600 hydrogen-oxygen nitrogen
Analyzer (LECO, the U.S.), each product, which is repeated three times, to be averaged.
In following embodiment, comparative example, using electron tubes type sintering furnace, the model HTO- of electron tubes type sintering furnace
114II, the heating rate in vacuum activating and step of hydrogenation are controlled in 10 DEG C/min.
Embodiment 1
The step of the present embodiment, is as follows successively：
(1) vacuum activating
Using sponge zirconium as raw material, the spectrogram that diffuses outside surface red is shown in Fig. 2, and sponge zirconium is placed in electron tubes type sintering furnace
In, control vacuum degree≤1.0 × 10 in stove-2It heats up after Pa, 30min, heating and heat preservation is kept the temperature when in-furnace temperature rises to 150 DEG C
Process keeps vacuum system to work, and makes vacuum degree≤1.0 × 10 in stove-2Pa after heat preservation, closes vacuum system, will live
Sponge zirconium block after change cools to room temperature with the furnace, carries out examination of infrared spectrum, and diffuse spectrogram such as Fig. 2 institutes outside surface red
Show；
(2) it hydrogenates
After vacuum activating, high-purity hydrogen is passed through into vacuum sintering furnace, when in stove air pressure reach 120KPa after heat up, work as stove
When interior temperature rises to 450 DEG C, 20min is kept the temperature, release and room temperature is cooled to the furnace after heat preservation, obtains zircoium hydride block, is risen
It is 120KPa, purity >=99.999% of the hydrogen that air pressure in stove is kept in mild insulating process；
(3) H, O content measure
H, O content measurement, hydrogen content 1.87wt.% are carried out to the zircoium hydride block that step (2) obtains, oxygen content is
0.28wt.%.
Comparative example 1
The step of this comparative example, is as follows：
(1) it hydrogenates
Using 1 identical sponge zirconium of embodiment as raw material, sponge zirconium is placed in electron tubes type sintering furnace, argon purge is passed through
After furnace body, then be passed through high-purity hydrogen, when in stove air pressure reach 120KPa after heat up, when in-furnace temperature rises to 500 DEG C, heat preservation
20min release and cools to room temperature with the furnace after heat preservation, obtains zircoium hydride block, stove is kept in heating and insulating process
Interior air pressure is 120KPa, purity >=99.999% of the hydrogen；
(2) H, O content measure
H, O content measurement, hydrogen content 1.82wt.% are carried out to the zircoium hydride block that step (1) obtains, oxygen content is
0.38wt.%.
The ZrH that embodiment 1 obtains2The ZrH obtained with comparative example 12It compares, hydrogen-sucking amount improves, and oxygen content reduces, and in hydrogen
Change pressure, time under the same conditions, hydrogenation temperature reduces by 50 DEG C.
Embodiment 2
The step of the present embodiment, is as follows successively：
(1) vacuum activating
Using sponge zirconium as raw material, stereoscan photograph is shown in Fig. 1 (a), and the spectrogram that diffuses outside surface red is shown in Fig. 2, will
Sponge zirconium is placed in electron tubes type sintering furnace, controls vacuum degree≤1.0 × 10 in stove-2It heats up after Pa, when in-furnace temperature rises to 300
DEG C when keep the temperature 30min, heating and insulating process keep vacuum system work, make vacuum degree≤1.0 × 10 in stove-2Pa, heat preservation
After, close vacuum system, cool to the sponge zirconium block after activation with the furnace room temperature, be scanned Electronic Speculum test and it is infrared
Diffuse reflectance spectroscopy, shown in stereoscan photograph such as Fig. 1 (b), the spectrogram that diffuses outside surface red is as shown in Figure 2；
(2) it hydrogenates
After vacuum activating, high-purity hydrogen is passed through into vacuum sintering furnace, when in stove air pressure reach 150KPa after heat up, work as stove
When interior temperature rises to 540 DEG C, 20min is kept the temperature, release and room temperature is cooled to the furnace after heat preservation, obtains zircoium hydride block,
Stereoscan photograph as shown in Figure 1, it is 150KPa to keep in stove air pressure in heating and insulating process, the purity of the hydrogen >=
99.999%；
(3) H, O content measure
H is carried out to the zircoium hydride block that step (2) obtains, O content measures, hydrogen content 2.14wt.%, oxygen content
0.16wt.%.
Comparative example 2
The step of this comparative example, is as follows：
(1) it hydrogenates
Using 2 identical sponge zirconium of embodiment as raw material, sponge zirconium is placed in electron tubes type sintering furnace, argon purge is passed through
After furnace body, then be passed through high-purity hydrogen, when in stove air pressure reach 150KPa after heat up, when in-furnace temperature rises to 540 DEG C, heat preservation
20min release and cools to room temperature with the furnace after heat preservation, obtains zircoium hydride block, stove is kept in heating and insulating process
Interior air pressure is 150KPa, purity >=99.999% of the hydrogen；
(2) H, O content measure
H, O content measurement, hydrogen content 1.86wt.% are carried out to the zircoium hydride block that step (1) obtains, oxygen content is
0.33wt.%.
Embodiment 2 is identical as the process conditions of 2 step of hydrogenation of comparative example, but the ZrH obtained2Hydrogen content and oxygen content difference
ZrH very big, that embodiment 2 obtains2Hydrogen content greatly improves and close to theoretical value (2.145wt.%), oxygen content is effectively controlled
System, and the ZrH that comparative example 2 obtains2Hydrogen content is larger compared with theoretical value gap, and oxygen content is higher.Show that vacuum activating can make
Sponge zirconium is inhaled hydrogen point and is shifted to an earlier date, and hydrogen-sucking amount and effectively control oxygen content are improved.
Embodiment 3
The step of the present embodiment, is as follows successively：
(1) vacuum activating
Using sponge zirconium as raw material, sponge zirconium is placed in electron tubes type sintering furnace, controls vacuum degree≤1.0 × 10 in stove- 2It heats up after Pa, 60min is kept the temperature when in-furnace temperature rises to 300 DEG C, heating and insulating process keep vacuum system to work, make
Vacuum degree≤1.0 × 10 in stove-2Pa；
(2) it hydrogenates
After vacuum activating, high-purity hydrogen is passed through into vacuum sintering furnace, when in stove air pressure reach 180KPa after heat up, work as stove
When interior temperature rises to 540 DEG C, 20min is kept the temperature, release and room temperature is cooled to the furnace after heat preservation, obtains zircoium hydride block, is risen
It is 180KPa, purity >=99.999% of the hydrogen that air pressure in stove is kept in mild insulating process；
(3) H, O content measure
H, O content measurement, hydrogen content 2.12wt.% are carried out to the zircoium hydride block that step (2) obtains, oxygen content is
0.18wt.%.
Comparative example 3
The step of this comparative example, is as follows：
(1) it hydrogenates
Using 3 identical sponge zirconium of embodiment as raw material, sponge zirconium is placed in electron tubes type sintering furnace, argon purge is passed through
After furnace body, then be passed through high-purity hydrogen, when in stove air pressure reach 180KPa after heat up, when in-furnace temperature rises to 700 DEG C, heat preservation
20min release and cools to room temperature with the furnace after heat preservation, obtains zircoium hydride block, stove is kept in heating and insulating process
Interior air pressure is 180KPa, purity >=99.999% of the hydrogen；
(2) H, O content measure
H, O content measurement, hydrogen content 1.99wt.% are carried out to the zircoium hydride block that step (1) obtains, oxygen content is
0.40wt.%.
The ZrH that embodiment 3 obtains2The ZrH obtained with comparative example 32It compares, hydrogen-sucking amount significantly improves, and oxygen content significantly drops
It is low, and hydrogenation pressure, time under the same conditions, hydrogenation temperature reduce by 160 DEG C.Show that vacuum activating can be such that sponge zirconium inhales
Hydrogen point shifts to an earlier date, and hydrogenation temperature reduces, and avoids ZrH2It decomposes.
Embodiment 4
The step of the present embodiment, is as follows successively：
(1) vacuum activating
Using sponge zirconium as raw material, sponge zirconium is placed in electron tubes type sintering furnace, controls vacuum degree≤1.0 × 10 in stove- 2It heats up after Pa, 30min is kept the temperature when in-furnace temperature rises to 350 DEG C, heating and insulating process keep vacuum system to work, make
Vacuum degree≤1.0 × 10 in stove-2Pa；
(2) it hydrogenates
After vacuum activating, high-purity hydrogen is passed through into vacuum sintering furnace, when in stove air pressure reach 180KPa after heat up, work as stove
When interior temperature rises to 600 DEG C, 10min is kept the temperature, release and room temperature is cooled to the furnace after heat preservation, obtains zircoium hydride block, is risen
It is 180KPa, purity >=99.999% of the hydrogen that air pressure in stove is kept in mild insulating process；
(3) H, O content measure
H, O content measurement, hydrogen content 2.04wt.% are carried out to the zircoium hydride block that step (2) obtains, oxygen content is
0.17wt.%.
Comparative example 4
The step of this comparative example, is as follows：
(1) it hydrogenates
Using 4 identical sponge zirconium of embodiment as raw material, sponge zirconium is placed in electron tubes type sintering furnace, argon purge is passed through
After furnace body, then be passed through high-purity hydrogen, when in stove air pressure reach 180KPa after heat up, when in-furnace temperature rises to 700 DEG C, heat preservation
10min release and cools to room temperature with the furnace after heat preservation, obtains zircoium hydride block, stove is kept in heating and insulating process
Interior air pressure is 180KPa, purity >=99.999% of the hydrogen；
(2) H, O content measure
H, O content measurement, hydrogen content 1.94wt.% are carried out to the zircoium hydride block that step (1) obtains, oxygen content is
0.37wt.%.
The ZrH that embodiment 4 is obtained2The ZrH obtained with comparative example 42It compares, after vacuum activating, close to identical suction
In the case of hydrogen amount, hydrogenation can carry out at lower temperatures, and oxygen content is effectively controlled.Show that vacuum activating can make
Sponge zirconium is inhaled hydrogen point and is shifted to an earlier date, and hydrogenation temperature and control oxygen content are reduced.
Embodiment 5
The step of the present embodiment, is as follows successively：
(1) vacuum activating
Using zircaloy bits as raw material, by zircaloy bits be placed in electron tubes type sintering furnace, control stove in vacuum degree≤1.0 ×
10-2It heating up after Pa, 30min is kept the temperature when in-furnace temperature rises to 300 DEG C, heating and insulating process keep vacuum system to work,
Make vacuum degree≤1.0 × 10 in stove-2Pa；
(2) it hydrogenates
After vacuum activating, high-purity hydrogen is passed through into vacuum sintering furnace, when in stove air pressure reach 160KPa after heat up, work as stove
When interior temperature rises to 650 DEG C, 20min is kept the temperature, release and room temperature is cooled to the furnace after heat preservation, obtains zircoium hydride block, is risen
It is 160KPa, purity >=99.999% of the hydrogen that air pressure in stove is kept in mild insulating process；
(3) H, O content measure
H, O content measurement, hydrogen content 2.09wt.% are carried out to the zircoium hydride block that step (2) obtains, oxygen content is
0.30wt.%.
Comparative example 5
The step of this comparative example, is as follows：
(1) it hydrogenates
It is considered to be worth doing as raw material with 5 identical zircaloy of embodiment, zircaloy bits is placed in electron tubes type sintering furnace, argon gas is passed through
After cleaning furnace body, then be passed through high-purity hydrogen, when in stove air pressure reach 160KPa after heat up, when in-furnace temperature rises to 650 DEG C, protect
Warm 20min release and cools to room temperature with the furnace after heat preservation, obtains zircoium hydride block, is kept in heating and insulating process
Air pressure is 160KPa, purity >=99.999% of the hydrogen in stove；
(2) H, O content measure
H, O content measurement, hydrogen content 1.93wt.% are carried out to the zircoium hydride block that step (1) obtains, oxygen content is
0.46wt.%.
Embodiment 5 is identical as the process conditions of 5 step of hydrogenation of comparative example, but the ZrH obtained2Hydrogen content and oxygen content are not
Together, the ZrH that embodiment 5 obtains2Hydrogen content is 2.09wt.%, oxygen content 0.30wt.%, and the ZrH that comparative example 5 obtains2Contain
Hydrogen amount is 1.93wt.%, oxygen content 0.46wt.%.Show that vacuum activating can make zircaloy bits inhale hydrogen point and shift to an earlier date, improves and inhale
Hydrogen amount and effectively control oxygen content.
Embodiment 6
The step of the present embodiment, is as follows successively：
(1) vacuum activating
Using zircaloy bits as raw material, by zircaloy bits be placed in electron tubes type sintering furnace, control stove in vacuum degree≤1.0 ×
10-2It heating up after Pa, 90min is kept the temperature when in-furnace temperature rises to 150 DEG C, heating and insulating process keep vacuum system to work,
Make vacuum degree≤1.0 × 10 in stove-2Pa；
(2) it hydrogenates
After vacuum activating, high-purity hydrogen is passed through into vacuum sintering furnace, when in stove air pressure reach 140KPa after heat up, work as stove
When interior temperature rises to 500 DEG C, 30min is kept the temperature, release and room temperature is cooled to the furnace after heat preservation, obtains zircoium hydride block, is risen
It is 140KPa, purity >=99.999% of the hydrogen that air pressure in stove is kept in mild insulating process；
(3) H, O content measure
H, O content measurement, hydrogen content 1.92wt.% are carried out to the zircoium hydride block that step (2) obtains, oxygen content is
0.34wt.%.
Claims (3)
1. a kind of zirconium and the method for zircaloy hydrogenation process optimization, it is characterised in that this method is increased before zirconium or zircaloy hydrogenation
Add vacuum activating step, processing step as follows successively：
(1) vacuum activating
Zirconium or zircaloy are placed in vacuum sintering furnace, vacuum degree≤1.0 × 10 in stove are controlled-2It heats up after Pa, works as in-furnace temperature
30~90min is kept the temperature when rising to 150~350 DEG C, and vacuum degree≤1.0 × 10 in stove are kept in heating and insulating process-2Pa；
(2) it hydrogenates
After vacuum activating, it is passed through high-purity hydrogen into vacuum sintering furnace and carries out hydrogenation treatment, the purity of the hydrogen >=
99.999%.
2. zirconium and the method for zircaloy hydrogenation process optimization according to claim 1, it is characterised in that step (2) described hydrogenation
The operation of processing is：When in stove air pressure reach 120~180KPa after heat up, when in-furnace temperature rises to 450~650 DEG C, heat preservation
10~30min release and cools to room temperature with the furnace after heat preservation, obtains hydrogenation zirconia material, is protected in heating and insulating process
It is 120~180KPa to hold air pressure in stove,.
3. zirconium according to claim 1 or claim 2 and the method for zircaloy hydrogenation process optimization, it is characterised in that the form of the zirconium
Form for sponge zirconium, zircaloy is zirconium alloy pipe, zirconium alloy bar, airconium alloy plates or zircaloy bits.
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| CN114749672A (en) * | 2022-03-30 | 2022-07-15 | 有研工程技术研究院有限公司 | Preparation method and application of high-purity ZrAl1 powder |
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| CN112899609A (en) * | 2019-11-19 | 2021-06-04 | 国核锆铪理化检测有限公司 | Zirconium and zirconium alloy quantitative hydrogen content hydrogen permeating method and hydrogen permeating piece |
| CN112899610A (en) * | 2019-11-19 | 2021-06-04 | 国核锆铪理化检测有限公司 | Zirconium and zirconium alloy hydrogen permeating device |
| CN113501716A (en) * | 2021-07-13 | 2021-10-15 | 西安稀有金属材料研究院有限公司 | Preparation method of crack-free zirconium hydride neutron moderating material |
| CN114749672A (en) * | 2022-03-30 | 2022-07-15 | 有研工程技术研究院有限公司 | Preparation method and application of high-purity ZrAl1 powder |
| CN114749672B (en) * | 2022-03-30 | 2023-08-15 | 有研工程技术研究院有限公司 | Preparation method and application of high-purity ZrAl1 powder |
| CN117292852A (en) * | 2023-11-27 | 2023-12-26 | 西安稀有金属材料研究院有限公司 | Zirconium hydride moderating material and preparation method thereof |
| CN117292852B (en) * | 2023-11-27 | 2024-03-08 | 西安稀有金属材料研究院有限公司 | Zirconium hydride moderating material and preparation method thereof |
| CN117884637A (en) * | 2024-03-12 | 2024-04-16 | 西安理工大学 | Forming method of metal hydride and high-vacuum cooperative oxygen control integral contact and contact |
| CN117884637B (en) * | 2024-03-12 | 2024-05-28 | 西安理工大学 | Forming method of metal hydride and high-vacuum cooperative oxygen control integral contact and contact |
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