CN100386337C - Method for in-situ synthesizing preparation of high-purity GdH2 block material - Google Patents
Method for in-situ synthesizing preparation of high-purity GdH2 block material Download PDFInfo
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- CN100386337C CN100386337C CNB2006100020532A CN200610002053A CN100386337C CN 100386337 C CN100386337 C CN 100386337C CN B2006100020532 A CNB2006100020532 A CN B2006100020532A CN 200610002053 A CN200610002053 A CN 200610002053A CN 100386337 C CN100386337 C CN 100386337C
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Abstract
The present invention belongs to the field of hydride material preparation. Ordinary rare earth hydride only exists in the powder form, and hydride with single component is difficult to obtain. The present invention comprises the following steps: a hydrogen electric arc plasma device is used; pure gadolinium is used as an anode and metal wolframium is used as a cathode; the volume ratio of hydrogen gas to argon gas is from 0.2 to 0.8, and the total pressure is from 100 to 650 torr; the arc current is from 50 to 150A, the arc voltage is from 10 to 50V and the arcing time is from 0.5 to 2 hours; hydride nanometer particles of gadolinium are prepared and are put into a preprocessing chamber with high purity argon gas protection; a graphite mold is assembled for prepressing formation, and the pressure is from 10 to 30MPa. Green bodies formed by prepressing formation are sintered by discharging plasmas; the sintering parmeter is that the sintering temperature is from 750 to 900 DEG C, the pressure is from 30 to 50MPa, the sintering pulse ratio is 1: 12 and the rate of temperature rise is from 50 to 80 DEG C /min; and samples are sintered and cooled by following furnaces to obtain GdH2 block materials with high purity. The hydride block material of rare earth gadolinium elements has the advantages of good microstructure and higher purify.
Description
Technical field
A kind of original position is synthesized high-purity GdH
2The preparation method of block materials belongs to the hydride material preparing technical field.
Background technology
Because rare earth hydride can have a wide range of applications at aspects such as optical window, hydrogen sensor, crystal indicating meter, pressure actuator, Chu Qing, become one of focus of new function material research.
Because rare earth element character is active, oxidation easily takes place, so rare earth hydride can only prepare under UHV condition usually in atmosphere.Rare earth element inhales behind the hydrogen then that volume expands and causes efflorescence, so general rare earth hydride can only exist with form of powder, and the rare earth hydride material of preparation is based on film, and its thickness is in the range scale of nanometer.Simultaneously, prepared rare earth hydride all is to exist with the hydride of non-stoichiometric, is difficult to the hydride of the stoichiometric ratio of acquisition single component.These situations have limited the industrial application of rare earth hydride material greatly.Therefore, preparation and exploitation single component high-purity rare-earth hydride block become the emphasis of this class material practicability.
At above-mentioned present Research, the present invention is under whole original positions, oxygen free condition, adopt hydrogen arc plasma process (Hydrogen Plasma Metal Reaction, HPAM) with discharge plasma sintering (SparkPlasma Sintering, the preparation of the HPAM-SPS technology success that SPS) combines the hydride GdH of high-purity rare-earth gadolinium
2Block, this has opened up a new way for preparation rare earth hydride block materials.It provides a platform for research rare earth hydride block materials, can be the performance (as sound, light, electromagnetism and thermodynamic behaviour) that other scientific workers study the rare earth hydride material condition is provided.
Summary of the invention
The present invention is directed to the problem that exists in the above-mentioned technology, provide a kind of hydrogen arc plasma device that utilizes the original position anaerobic to prepare the hydride nano-particle of gadolinium, utilize discharge plasma sintering technique to sinter the hydride nano-particle of gadolinium into high-purity GdH then
2The preparation method of block materials.Purpose is to obtain high-purity GdH of single component stoichiometric ratio
2Block materials.
The high-purity GdH of the synthetic preparation of a kind of original position provided by the invention
2The method of block materials is characterized in that, may further comprise the steps:
1) utilizes hydrogen arc plasma device, with pure gadolinium as anode, tungsten is as negative electrode, under the mixed atmosphere of hydrogen and argon gas, hydrogen and argon gas volume ratio are 0.2-0.8, and total pressure 13332.9-86663.85Pa selects flame current 50-150A, arc voltage 10-50V, the hydride nano-particle of arcing time 0.5-2 hour preparation rare-earth element gadolinium;
2) hydride nano-particle of above-mentioned gadolinium is inserted the pretreatment chamber of argon gas body protection, with nanometer hydrogenation gadolinium powder pack into graphite jig and pre-molding, pressure 10-30MPa;
3) with the hydride nano-particle green compact plasma discharging Fast Sintering of above-mentioned rare-earth element gadolinium through pre-molding, concrete sintering process parameter is: sintering temperature is 750-900 ℃, sintering pressure is 30-50Mpa, and the sintering ratio of pulse length to the total cycle length is 1: 12, and the sintering temperature rise rate is 50-80 ℃/min; The intact sample of sintering obtains having highly purified GdH with the stove naturally cooling
2Block materials.
The hydride block materials of the rare earth gadolinium element of employing method for preparing provided by the invention has good microstructure, and the GdH for preparing
2The purity of block materials is higher.Therefore be a kind of high-quality GdH that obtains
2The preparation method of block materials.
Description of drawings
Fig. 1: the X ray diffracting spectrum (embodiment 1) of the hydride nano-particle of the rare-earth element gadolinium of employing hydrogen arc plasma device preparation.
Fig. 2: hydride nanometer monocrystalline particulate shape appearance figure Fig. 2 (a) (transmission electron microscope photo) of the rare-earth element gadolinium of employing hydrogen arc plasma device preparation and electron diffraction pattern Fig. 2 (b) (embodiment 1) of single crystal grain thereof.
Fig. 3: the high-purity GdH that adopts the discharge plasma sintering technique preparation
2The X ray diffracting spectrum of block materials (embodiment 1).
Fig. 4: the high-purity GdH that adopts the discharge plasma sintering technique preparation
2Electron diffraction pattern Fig. 4 (b) (embodiment 1) of Fig. 4 of micro-organization chart (a) of the material of block (high explanation transmission electron microscope photo) and single crystal grain thereof.
Fig. 5: the high-purity GdH that adopts the discharge plasma sintering technique preparation
2The atomic lattice picture of the material of block (high explanation transmission electron microscope photo) (embodiment 1).
Fig. 6: the high-purity GdH that adopts the discharge plasma sintering technique preparation
2The X ray diffracting spectrum of block materials (embodiment 2).
Fig. 7: the high-purity GdH that adopts the discharge plasma sintering technique preparation
2The X ray diffracting spectrum of block materials (embodiment 3).
Embodiment
Example 1, high-purity gadolinium are put hydrogen arc plasma device, and (diameter 5mm) makes negative electrode with tungsten bar, and the reguline metal gadolinium is made anode.At first vacuum chamber is evacuated to 10
-4Pa charges into the mixed gas of hydrogen and argon gas then, and hydrogen and argon gas volume ratio are 0.2, and total pressure is 13332.9Pa.Connect direct supply, control reaction current about flame current 50A, arc voltage 20V, scratch start became feedstock production in 0.5 hour the hydride nano-particle of rare-earth element gadolinium.With the nano particle of above-mentioned gadolinium at pretreatment chamber's powder of high purity inert gas protection pack into graphite jig and pre-molding.Preload pressure 10MPa.Utilize plasma discharging Fast Sintering technology (SPS-5.40-IV/ET type) to be sintered into GdH on green compact
2Block materials.Sintering process parameter is: sintering temperature is 750 ℃, and sintering pressure is 30MPa, and the sintering ratio of pulse length to the total cycle length is 1: 12, and the sintering temperature rise rate is 50 ℃/min, and the sintering atmosphere is a vacuum.Sintering finishes the sample furnace cooling.Specimen preparation is finished.Sample is tested and detected.Utilize X-ray diffractometer to check the hydride nano-particle of the gadolinium of hydrogen arc plasma device preparation, the X diffracting spectrum as shown in Figure 1, the material that can see its preparation is the hydride of gadolinium: cubical GdH
2GdH with six sides
3, do not have other phase.Utilize transmission electron microscope (TEM model JEOL 2010 transmission electron microscopes, acceleration voltage is 200KV) and electron diffraction that the hydride particle that hydrogen arc plasma device has prepared nano rare earth metal gadolinium is carried out observation analysis simultaneously, as shown in Figure 2.
Utilize X-ray diffractometer to detect plasma discharging Fast Sintering technology sintering GdH
2The thing phase of block, its X diffracting spectrum as shown in Figure 3, the diffraction peak that can see the block materials of its preparation is one cube of GdH of hydride of gadolinium
2Diffraction peak, just adopting the block materials of HPAM-SPS technology preparation is single component stoichiometric ratio GdH
2, do not have other phase.Adopt high-resolution electron microscope (HRTEM model PHILIPS TECNAIF30 field emission high-resolution-ration transmission electric-lens, acceleration voltage is 300KV) to observe plasma discharging Fast Sintering technology sintering GdH
2The microstructure of block and structure are shown in Fig. 4,5.The spacing of institute's mark is 3.067 dusts among Fig. 5, with a cube GdH
2(111) spacing 3.0660 dusts be consistent.
Example 2, high-purity gadolinium is put hydrogen arc plasma device, (diameter 5mm) makes negative electrode with tungsten bar, and the reguline metal gadolinium is made anode.At first vacuum chamber is evacuated to 10
-4Pa charges into the mixed gas of hydrogen and argon gas then, and hydrogen and argon gas volume ratio are 0.6, and total pressure is 39998.7Pa.Connect direct supply, control reaction current about flame current 100A, arc voltage 40V, scratch start became feedstock production in 1 hour the hydride nano-particle of rare-earth element gadolinium.With the nano particle of above-mentioned gadolinium at pretreatment chamber's powder of high purity inert gas protection pack into graphite jig and pre-molding.Preload pressure 20MPa.Utilize plasma discharging Fast Sintering technology (SPS-5.40-IV/ET type) to be sintered into GdH on green compact
2Block materials.Sintering process parameter is: sintering temperature is 800 ℃, and sintering pressure is 40MPa, and the sintering ratio of pulse length to the total cycle length is 1: 12, and the sintering temperature rise rate is 60 ℃/min, and the sintering atmosphere is an argon gas atmosphere.Sintering finishes the sample furnace cooling.Specimen preparation is finished.Sample is tested and detected.Utilize X-ray diffractometer to detect plasma discharging Fast Sintering technology sintering GdH
2The thing phase of block, its X diffracting spectrum as shown in Figure 6, the diffraction peak that can see the block materials of its preparation is one cube of GdH of hydride of gadolinium
2Diffraction peak.
Example 3, high-purity gadolinium is put hydrogen arc plasma device, (diameter 5mm) makes negative electrode with tungsten bar, and the reguline metal gadolinium is made anode.At first vacuum chamber is evacuated to 10
-4Pa charges into the mixed gas of hydrogen and argon gas then, and hydrogen and argon gas volume ratio are 0.8, and total pressure is 86663.85Pa.Connect direct supply, control reaction current about flame current 150A, arc voltage 50V, scratch start became feedstock production in 2 hours the hydride nano-particle of rare-earth element gadolinium.With the nano particle of above-mentioned gadolinium at pretreatment chamber's powder of high purity inert gas protection pack into graphite jig and pre-molding.Preload pressure 30MPa.Utilize plasma discharging Fast Sintering technology (SPS-5.40-IV/ET type) to be sintered into GdH on green compact
2Block materials.Sintering process parameter is: sintering temperature is 900 ℃, and sintering pressure is 50MPa, and the sintering ratio of pulse length to the total cycle length is 1: 12, and the sintering temperature rise rate is 50 ℃/min, and the sintering atmosphere is a vacuum.Sintering finishes the sample furnace cooling.Specimen preparation is finished.Sample is tested and detected.Utilize X-ray diffractometer to detect plasma discharging Fast Sintering technology sintering GdH
2The thing phase of block, its X diffracting spectrum as shown in Figure 7, the diffraction peak that can see the block materials of its preparation is one cube of GdH of hydride of gadolinium
2Diffraction peak.
Claims (1)
1. an original position is synthesized the high-purity GdH of preparation
2The method of block materials is characterized in that, may further comprise the steps:
1) utilize hydrogen arc plasma device, as anode, tungsten is as negative electrode with pure gadolinium; Under the mixed atmosphere of hydrogen and argon gas, hydrogen and argon gas volume ratio are between 0.2-0.8, and total pressure 13332.9-86663.85Pa scope is selected flame current 50-150A, arc voltage 10-50V, the hydride nano-particle of arcing time 0.5-2 hour preparation rare-earth element gadolinium;
2) hydride nano-particle of above-mentioned gadolinium is inserted the pretreatment chamber of argon gas body protection, with nanometer hydrogenation gadolinium powder pack into graphite jig and pre-molding, pressure range 10-30MPa;
3) with the hydride nano-particle green compact of above-mentioned rare-earth element gadolinium through pre-molding, utilize plasma discharging Fast Sintering technology that pressed compact is sintered into and have highly purified GdH
2Block materials, concrete sintering process parameter is: sintering temperature is 750-900 ℃, and sintering pressure is 30-50Mpa, and the sintering ratio of pulse length to the total cycle length is 1: 12, and the sintering temperature rise rate is 50-80 ℃/min; The intact sample of sintering is with the stove naturally cooling.
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| CN102730738B (en) * | 2012-06-12 | 2014-06-04 | 北京航空航天大学 | Preparation method of binary or multi-constituent composite rare earth oxide nanoparticles |
| CN103214042B (en) * | 2013-04-27 | 2015-11-18 | 中国科学院金属研究所 | A kind of superparamagnetic rare earth intermetallic compound nano particle and preparation method thereof |
| CN103409650B (en) * | 2013-07-25 | 2014-11-12 | 北京大学 | Novel method for utilizing hydrogen plasma electric arc melting technology to prepare high-purity rare earth gadolinium elementary substance |
| KR102270863B1 (en) | 2013-09-25 | 2021-06-30 | 다이헤이요 세멘토 가부시키가이샤 | Method for producing metal hydride |
| CN104291270B (en) * | 2014-07-02 | 2016-05-11 | 北京理工大学 | A kind of high temperature direct method is prepared the method for light rare earth hydride |
| CN104923790B (en) * | 2014-11-25 | 2018-08-17 | 安泰科技股份有限公司 | A kind of gadolinium block materials and preparation method thereof |
| JP6973331B2 (en) * | 2018-08-27 | 2021-11-24 | 新東工業株式会社 | Method for producing tetrahydroborate, equipment for producing tetrahydroborate and tetrahydroborate |
| CN113005310B (en) * | 2021-02-23 | 2022-07-22 | 昆明理工大学 | Method for purifying rare earth metal gadolinium and preparing gadolinium oxide nano material by arc plasma method |
| CN113969361B (en) * | 2021-10-27 | 2023-05-16 | 中国核动力研究设计院 | Preparation method of high-purity yttrium, preparation method of yttrium hydride pellet and yttrium hydride pellet |
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| CN1517297A (en) * | 2003-01-19 | 2004-08-04 | 辽宁师范大学 | Method of synthesizing nanometer size lanthanum-series metal hydride by activating lanthanum metal and using solvent effect |
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| CN1517297A (en) * | 2003-01-19 | 2004-08-04 | 辽宁师范大学 | Method of synthesizing nanometer size lanthanum-series metal hydride by activating lanthanum metal and using solvent effect |
Non-Patent Citations (2)
| Title |
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| 我国金属氢化物化学研究. 袁华堂等.化学通报，第11期. 1999 |
| 我国金属氢化物化学研究. 袁华堂等.化学通报，第11期. 1999 * |
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