CN103482571B - Preparation method and device for beryllium hydride material - Google Patents
Preparation method and device for beryllium hydride material Download PDFInfo
- Publication number
- CN103482571B CN103482571B CN201310441492.3A CN201310441492A CN103482571B CN 103482571 B CN103482571 B CN 103482571B CN 201310441492 A CN201310441492 A CN 201310441492A CN 103482571 B CN103482571 B CN 103482571B
- Authority
- CN
- China
- Prior art keywords
- beryllium
- tert
- preparation
- beryllium hydride
- butyl
- 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.)
- Expired - Fee Related
Links
Landscapes
- Filling Or Discharging Of Gas Storage Vessels (AREA)
- Chemical Vapour Deposition (AREA)
- Silicon Compounds (AREA)
Abstract
The invention provides a preparation method and device for a beryllium hydride material. According to the device, reactive hydrogen atom jet flows are formed by restraining low-pressure hydrogen plasmas so as to induce di-tert-butyl beryllium gas molecules to generate gaseous beryllium hydride molecules through gas phase schizolysis; then a beryllium hydride film or beryllium hydride powder is formed by collision and polymerization of the beryllium hydride molecules. According to the invention, as active hydrogen atoms can rupture Be-C bonds in the beryllium hydride molecules, and have no obvious influence on C-C bonds, and the number of hydrogen atoms is obviously excessive than that of beryllium atoms, so that the beryllium hydride material with relatively high purity can be obtained by adopting the preparation method and device.
Description
Technical field
The present invention relates to a kind of preparation method and device of beryllium hydride material, more particularly, the present invention relates to a kind of active hydrogen atom that adopts and induce Di-tert-butyl beryllium vapor-phase thermal cracking prepare the method for beryllium hydride material and realize the device of the method.
Background technology
Beryllium hydride is a kind of high-performance solid hydrogen storage material, and storage hydrogen mass percent is 18.28%, higher than conventional solid hydrogen storage material lithium hydride (LiH, 12.68%), magnesium hydride (MgH
2, 7.66%) and aluminum hydride (AlH
3, 10.08%), heating will discharge hydrogen a little.Meanwhile, the volume hydrogen-storage density of beryllium hydride is 7.12 × 10
22atom/cm
3, be 2 times (4.22 × 10 of the solid hydrogen of 11K close to temperature
22atom/cm
3).In addition, beryllium hydride or a kind of required raw material preparing the materials such as foam beryllium, nanometer beryllium and amorphous beryllium.
Some bibliographical informations adopt direct pyrolysis (the J. Chem. Soc. of Di-tert-butyl beryllium, 2526 (1954)), solution pyrolysis (copending application Ser. No. 176865, filed Feb 26,1962) and vacuum gas-phase pyrolysis (US Patent 3743710, July 3,1973) etc. method prepare beryllium hydride material (powder or film).Due to the thermolability of Di-tert-butyl beryllium, its pyrolysis temperature range interval narrower (200 ± 5 DEG C), be difficult to prepare the higher beryllium hydride material of purity (powder or film), or in preparation technology, implement difficulty larger.When pyrolysis temperature is lower than 185 DEG C, easily there is intermolecular disproportionation reaction in Di-tert-butyl beryllium, incomplete decomposing becomes alkyl beryllium; When pyrolysis temperature is higher than 210 DEG C, easily overheatedly resolve into metallic beryllium (Be), and pyrolysis method is applicable to preparing beryllium hydride powder, is difficult to prepare beryllium hydride film.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of preparation method of beryllium hydride material.
Another technical problem that will solve of the present invention is to provide a kind of preparation facilities of beryllium hydride material, and this device produces hydrogen plasma, retrains and obtains active hydrogen atom jet, and induction Di-tert-butyl beryllium vapor-phase thermal cracking prepares beryllium hydride material.
The preparation method of beryllium hydride material of the present invention, comprises the following steps successively:
A () low pressure hydrogen produces hydrogen plasma under radio frequency inductive coupled discharge condition;
B () retrains hydrogen plasma, obtain active hydrogen atom jet;
C active hydrogen atom and Di-tert-butyl beryllium steam are imported hybrid reaction chamber crash response by (), active hydrogen atom induction Di-tert-butyl beryllium molecular vapor cracking also generates gaseous hydro beryllium molecule;
D () gaseous hydro beryllium molecular impact aggregates into solid-state beryllium hydride material.
The air pressure of low pressure hydrogen described in step (a) is 1 ~ 100pa.
Retraining hydrogen plasma described in step (b) is that the sealing of foraminate metal sheet is opened at a center, the lower end of electric discharge silica tube, high-energy electron and ion are limited in silica tube, and active hydrogen atom injects reaction chamber induction Di-tert-butyl beryllium vapor-phase thermal cracking by this aperture.
The carrier gas importing Di-tert-butyl beryllium steam described in step (c) is high-purity hydrogen, its purity >=99.995%.
The air pressure of active hydrogen atom described in step (c) and Di-tert-butyl beryllium steam crash response is 5.0 × 10
-2pa ~ 100Pa.
Beryllium hydride material described in step (d) is beryllium hydride film or beryllium hydride powder.
The preparation facilities of a kind of beryllium hydride material of the present invention, be characterized in: the hydrogen cylinder (1) in described device is divided into two-way after water filter (2), one road is used as carrier gas, one road is used as electric discharge hydrogen, by stainless steel tube (18) respectively with steel cylinder (7) inlet mouth, silica tube (17) connects, steel cylinder (7) air outlet is connected with hybrid reaction chamber (14), vacuum chamber (15) is communicated with by aperture with silica tube (17), vacuum chamber (15) is by a flange port and vacuum pump (12), filter vat (11) connects, described electric discharge silica tube (17) is communicated with hybrid reaction chamber (14) by aperture, active hydrogen atom imports hybrid reaction chamber (14) induction Di-tert-butyl beryllium vapor-phase thermal cracking by this aperture.
The diameter of described aperture is 2.5mm, and length is 4mm.
The preparation facilities working process of beryllium hydride material of the present invention is: high-purity hydrogen is divided into two-way after water filter dewaters.One road hydrogen controls the laggard silica tube that enters to discharge of flow through mass flow controller.Access radio-frequency voltage in radio frequency discharge telefault after, hydrogen glow discharge in electric discharge silica tube forms pressure hydrogen plasma body.After an aperture (φ 2.5 × 4mm) constraint, produce active hydrogen atom jet beam and inject hybrid reaction chamber.Another road hydrogen is as carrier gas, control to pass in steel cylinder after flow through mass flow controller, adopt the mode of bubbling to carry Di-tert-butyl beryllium steam and enter hybrid reaction chamber, collide also cracking with active hydrogen atom and generate beryllium hydride molecule, finally become beryllium hydride film at deposition on substrate or be condensed into beryllium hydride powder in the gas phase.
Beryllium hydride material preparation method provided by the invention preparation method relatively in the past has a lot of significantly advantage, and active hydrogen atom can by Be-C bond rupture in Di-tert-butyl beryllium, and induction Di-tert-butyl beryllium is cracked into beryllium hydride, and does not significantly affect C-C key.Solve pyrolysis method incomplete decomposing become alkyl beryllium and cross the problem resolving into metallic beryllium, therefore can obtain the higher beryllium hydride material of purity.The method simple and convenient, both can prepare beryllium hydride powder, also can depositing hydrogenated beryllium film.
Accompanying drawing explanation
Fig. 1 is the structural representation of beryllium hydride material preparation facilities of the present invention;
In figure: 1. hydrogen cylinder 2. water filter 3. first high vacuum valve 4. first mass flow controller 5. second high vacuum valve 6. constant temperature water bath device 7. steel cylinder 8. third high vacuum valve 9. the 4th high vacuum valve 10. the 5th high vacuum valve 11. tail gas filtering bucket 12. vacuum pump 13. sample table 14. hybrid reaction chamber 15. vacuum reaction chamber 16. telefault 17. silica tube 18. stainless steel tube 19. second mass flow controller 20. the 6th high vacuum valve.
Embodiment
Below in conjunction with drawings and Examples, preparation method of the present invention and device are further described.
Fig. 1 is the structural representation of the preparation facilities of beryllium hydride material of the present invention.
The preparation facilities of beryllium hydride material of the present invention comprises hydrogen cylinder 1, water filter 2, stainless steel tube 18 and the first to the 6th high vacuum valve 3, 5, 8, 9, 10, 20, first, second gas flow controller 4, 19, the steel cylinder 7 of Di-tert-butyl beryllium is housed, control the constant temperature water bath device 6 of temperature of reaction, hybrid reaction chamber 14, for generation of telefault 16 and the silica tube 17 of hydrogen plasma, vacuum chamber 15, vacuum pump 12, sample table 13, absorb the filter vat 11 of residual Di-tert-butyl beryllium in tail gas, described hydrogen cylinder 1 is divided into two-way after water filter 2, one road is used as carrier gas, one road is used as electric discharge hydrogen, by stainless steel tube 18 respectively with steel cylinder 7 inlet mouth, silica tube 17 connects, steel cylinder 7 air outlet is connected with hybrid reaction chamber 14, vacuum chamber 15 is communicated with by aperture with silica tube 17, vacuum chamber 15 is by a flange port and vacuum pump 12, filter vat 11 connects.Described steel cylinder 7 is placed in constant temperature water bath device 6, is controlled temperature and the saturated vapor pressure of Di-tert-butyl beryllium, then jointly control the transfer rate of Di-tert-butyl beryllium steam in conjunction with carrier gas flux by constant temperature water bath device 6.
The preparation process of beryllium hydride material of the present invention:
A () is evacuated down to 4.0 × 10
-4pa, low pressure hydrogen produces hydrogen plasma under radio frequency inductive coupled discharge condition, and electric discharge air pressure is 1 ~ 100Pa, and RF source frequencies is 43.68MHz, and radio frequency source discharge power is 50 ~ 200W;
B () constraint hydrogen plasma, by high-energy electron and ion limit in silica tube, obtains active hydrogen atom jet;
C active hydrogen atom and Di-tert-butyl beryllium steam are imported hybrid reaction chamber crash response by (), active hydrogen atom induction Di-tert-butyl beryllium molecular vapor cracking also generates gaseous hydro beryllium molecule.The hydrogen flowing quantity of conveying Di-tert-butyl beryllium steam is 1 ~ 10sccm, and its purity>=99.995%, organic source temperature is 20 ~ 35 DEG C, and reaction pressure is 5.0 × 10
-2~ 100Pa;
D () gaseous hydro beryllium molecular impact aggregates into solid-state beryllium hydride material.When reaction pressure is lower, substrate obtains beryllium hydride film; When reaction pressure is higher, in gas phase, form beryllium hydride powder, install multiple layer metal silk fine-structure mesh additional at vacuum chamber bleeding point and collect beryllium hydride powder.
Embodiment 1
Below first to prepare beryllium hydride film, the specific embodiment of the present invention is described.Laboratory operating procedures mainly comprises following five steps:
The first step: vacuumize
Fixed placement silicon substrate in sample table, by the forvacuum of related for vacuum reaction chamber 15 distribution pipeline to 4.0 × 10
-4pa.
Second step: flushing pipeline
Open the first mass flow controller 4, second mass flow controller 19 and be set as 10 ml/min (sccm), then open the first high vacuum valve 3, the 6th high vacuum valve 20, the 5th high vacuum valve 10 and the 4th high vacuum valve 9, close the second high vacuum valve 5, third high vacuum valve 8 flushing pipeline 1hr.Di-tert-butyl beryllium is as easy as rolling off a log reacts with oxygen, water the highly toxic beryllium oxide solid dust generating white, therefore before conveying Di-tert-butyl beryllium, needs flushing pipeline, except anhydrating and oxygen.
3rd step: radio frequency discharge
Regulate the slide valve of vacuum chamber 15 to make the hydrogen gas pressure in electric discharge silica tube 17 be 30Pa, the hydrogen gas pressure in vacuum reaction chamber 15 is 7.5 × 10
-2pa.Open radio-frequency power supply, adjustment incident power is 180W, in electric discharge silica tube 17, form hydrogen plasma.What adopt in experiment is frequency tripling (43.68MHz) transistor radio-frequency power supply, after matching box regulates, power is loaded into spiral winding, excites rf electric field to form hydrogen plasma in silica tube.
4th step: sedimentation experiment
The temperature of constant temperature water bath device 6 is set as 25 DEG C, the 4th high vacuum valve 9 is closed after temperature-stable, open the second high vacuum valve 5 and third high vacuum valve 8, adopt hydrogen as carrier gas, after water filter drying, pass into steel cylinder bubbling, carry Di-tert-butyl beryllium steam to hybrid reaction chamber 14, generate gaseous hydro beryllium molecule after reacting with active hydrogen atom, deposition polymerization becomes beryllium hydride film.
5th step: flushing pipeline
After deposition 6hr, close the second high vacuum valve 5 and third high vacuum valve 8, open the 4th high vacuum valve 9, after flushing pipeline 1hr, close radio-frequency power supply, experimental procedure terminates.
Have height property due to beryllium with containing beryllium compound, testing full step must have strict safeguard procedures.This preparation process has three-layer protection system: the first layer safeguard system is special beryllium prevention room, laboratory seals, be equipped with exhausting exhaust system, laboratory is made to remain at negative pressure state, air-flow flows in laboratory from laboratory, prevents from being discharged to outside laboratory with air-flow containing beryllium dust material.Exhausting exhaust system air-flow, after filter tower filtration reaches discharging standards, enters air; Second layer safeguard system is equipment protection, and experimental installation is placed in shield cap, and air-flow flows to equipment from operator and discharges from exhausting system, prevents containing the effusion of beryllium dust material slave unit; Third layer safeguard system is personal protection, comprises protective clothing and respirator.In addition, Di-tert-butyl beryllium steam easily spreads, and has high toxicity, contacts vigorous reaction can occur with oxygen, water vapor, and therefore the gas distributing system strict seal of this preparation facilities, prevents Di-tert-butyl beryllium from revealing.Di-tert-butyl beryllium residual in tail gas is removed by filter vat 11.
Embodiment 2
Remove sample table 13, and set up a multilayer Gas in Ultra-thin Metal Wires filtering net at the bleeding point (i.e. the ingress of vacuum pump 12) of vacuum reaction chamber 15, regulate the reaction pressure of vacuum reaction chamber to 70Pa, other experiment condition is identical with embodiment 1.The beryllium hydride powder of white can be collected at wire screen place after experiment terminates.Experiment shows: when reaction pressure is lower, trends towards on substrate, form beryllium hydride film; When reaction pressure is higher, trend towards forming trickle beryllium hydride powder in the gas phase.
Claims (7)
1. a preparation method for beryllium hydride material, is characterized in that: described method comprises the following steps successively:
A () low pressure hydrogen produces hydrogen plasma under radio frequency inductive coupled discharge condition;
B () retrains hydrogen plasma, obtain active hydrogen atom jet;
C active hydrogen atom and Di-tert-butyl beryllium steam are imported hybrid reaction chamber crash response by (), active hydrogen atom induction Di-tert-butyl beryllium molecular vapor cracking also generates gaseous hydro beryllium molecule; The hydrogen flowing quantity of conveying Di-tert-butyl beryllium steam is 1 ~ 10sccm, and organic source temperature is 20 ~ 35 DEG C, and the air pressure of active hydrogen atom and Di-tert-butyl beryllium steam crash response is 5.0 × 10
-2pa ~ 100Pa;
D () gaseous hydro beryllium molecular impact aggregates into solid-state beryllium hydride material.
2. the preparation method of beryllium hydride material according to claim 1, is characterized in that: the air pressure of low pressure hydrogen described in step (a) is 1 ~ 100pa.
3. the preparation method of beryllium hydride material according to claim 1, it is characterized in that: retraining hydrogen plasma described in step (b) is that the sealing of foraminate metal sheet is opened at a center, the lower end of electric discharge silica tube, high-energy electron and ion are limited in silica tube, and active hydrogen atom injects reaction chamber induction Di-tert-butyl beryllium vapor-phase thermal cracking by this aperture.
4. the preparation method of beryllium hydride material according to claim 1, is characterized in that: the carrier gas importing Di-tert-butyl beryllium steam described in step (c) is high-purity hydrogen, its purity >=99.995%.
5. the preparation method of beryllium hydride material according to claim 1, is characterized in that: beryllium hydride material described in step (d) is beryllium hydride film or beryllium hydride powder.
6. the preparation facilities of a beryllium hydride material, it is characterized in that: the hydrogen cylinder (1) in described device is divided into two-way after water filter (2), one road is used as carrier gas, one road is used as electric discharge hydrogen, is connected respectively by stainless steel tube (18) with steel cylinder (7) inlet mouth, silica tube (17); Steel cylinder (7) air outlet is connected with hybrid reaction chamber (14), vacuum chamber (15) is communicated with by aperture with silica tube (17), vacuum chamber (15) is connected with vacuum pump (12), filter vat (11) by a flange port, described electric discharge silica tube (17) is communicated with hybrid reaction chamber (14) by aperture, and active hydrogen atom imports hybrid reaction chamber (14) induction Di-tert-butyl beryllium vapor-phase thermal cracking by this aperture.
7. prepare the preparation method of beryllium hydride material according to claim 6, it is characterized in that: the diameter of described aperture is 2.5mm, and length is 4mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310441492.3A CN103482571B (en) | 2013-09-26 | 2013-09-26 | Preparation method and device for beryllium hydride material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310441492.3A CN103482571B (en) | 2013-09-26 | 2013-09-26 | Preparation method and device for beryllium hydride material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103482571A CN103482571A (en) | 2014-01-01 |
| CN103482571B true CN103482571B (en) | 2015-04-01 |
Family
ID=49823244
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310441492.3A Expired - Fee Related CN103482571B (en) | 2013-09-26 | 2013-09-26 | Preparation method and device for beryllium hydride material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103482571B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105177508A (en) * | 2015-10-16 | 2015-12-23 | 中国工程物理研究院激光聚变研究中心 | Method and device for preparing beryllium hydride coating material |
| CN105728746A (en) * | 2016-05-11 | 2016-07-06 | 中国工程物理研究院激光聚变研究中心 | Preparing method of nano beryllium powder |
| CN106694905B (en) * | 2017-03-03 | 2019-09-03 | 中国工程物理研究院激光聚变研究中心 | The preparation method and preparation facilities of a kind of nanometer of beryllium powder |
| CN107824791B (en) * | 2017-11-24 | 2019-09-03 | 中国工程物理研究院激光聚变研究中心 | A kind of preparation method of foam beryllium material |
| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3883646A (en) * | 1967-12-28 | 1975-05-13 | Dow Chemical Co | Preparation of beryllium hydride |
| US6680042B1 (en) * | 2000-11-07 | 2004-01-20 | Hydro-Quebec | Method of rapidly carrying out a hydrogenation of a hydrogen storage material |
-
2013
- 2013-09-26 CN CN201310441492.3A patent/CN103482571B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3883646A (en) * | 1967-12-28 | 1975-05-13 | Dow Chemical Co | Preparation of beryllium hydride |
| US6680042B1 (en) * | 2000-11-07 | 2004-01-20 | Hydro-Quebec | Method of rapidly carrying out a hydrogenation of a hydrogen storage material |
Non-Patent Citations (2)
| Title |
|---|
| 张吉强,罗江山,罗柄池,吴卫东.《MOCVD》方法制备BeH2薄膜.《稀有金属材料与工程》.2012,第41卷(第8期),1483-1486. * |
| 罗江山,吴卫东,唐永建.《BeH2材料的制备及在ICF中的应用》.《强激光与离子束》.2006,第18卷(第1期),85-87. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103482571A (en) | 2014-01-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103482571B (en) | Preparation method and device for beryllium hydride material | |
| KR20210016610A (en) | Apparatus and method for manufacturing carbon nanotubes | |
| CN108439377B (en) | Device and method for cooperatively treating organic waste liquid and preparing graphene by using low-temperature plasma technology | |
| CA2733354A1 (en) | Plasma processes for producing silanes and derivatives thereof | |
| CN104961127A (en) | Method for preparing nano graphene powder by plasma chemical vapor synthesis | |
| CN107630203A (en) | A kind of method of normal pressure cold plasma deposited metal simple substance membrane | |
| CN102491289A (en) | Method for preparing nanoscale magnesium nitride powder | |
| JP2008038164A (en) | Plasma cvd apparatus | |
| CN104378901A (en) | Two-stage arc plasma torch | |
| CN106011786B (en) | Atmospheric pressure disperse electric discharge device and metal surface deposition class SiO2Film process | |
| Saleem et al. | Removal of toluene as a toxic VOC from methane gas using a non-thermal plasma dielectric barrier discharge reactor | |
| CN204145869U (en) | A kind of two stage electric arc plasma torch | |
| CN111261861B (en) | Method for continuously preparing high-purity carbon-silicon nano material | |
| Di et al. | Preparation of copper nanoparticles using dielectric barrier discharge at atmospheric pressure and its mechanism | |
| CN102010001A (en) | Preparation method of titanium dioxide cubic cone crystal | |
| CN204168581U (en) | A kind of plasma torch of two-step nozzle structure | |
| CN103101907A (en) | Graphene, and preparation method and application thereof | |
| Costa et al. | Preparation of nanoscale amorphous silicon based powder in a square-wave-modulated rf plasma reactor | |
| CN104985177B (en) | Method for preparing nanometer germanium particles with passivated surfaces | |
| CN113603093B (en) | Preparation method and equipment of micro silicon powder | |
| CN100494510C (en) | Method for synthesizing diamond film under low-temperature by micro-wave and plasma | |
| CN115418622A (en) | Boron-doped diamond electrode and preparation method and preparation device thereof | |
| CN104363690A (en) | Plasma torch of double-stage nozzle structure | |
| CN102849752A (en) | Preparation method of boron nano-particles | |
| CN104152869A (en) | Plasma thin film deposition device and deposition method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150401 Termination date: 20200926 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |