CN103769581A - Multielement composite rare earth electron emission material and preparation method thereof - Google Patents
Multielement composite rare earth electron emission material and preparation method thereof Download PDFInfo
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- CN103769581A CN103769581A CN201410059760.XA CN201410059760A CN103769581A CN 103769581 A CN103769581 A CN 103769581A CN 201410059760 A CN201410059760 A CN 201410059760A CN 103769581 A CN103769581 A CN 103769581A
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Abstract
The invention discloses a multi-element composite rare earth electron emission material and a preparation method thereof, belonging to the field of powder metallurgy. The preparation method of the material is also provided, and tungsten metal matrix powder, rare earth oxide and nitrate are used as raw materials; preparing mixed powder: adding deionized water into tungsten metal matrix powder to prepare suspension; preparing rare earth oxide and nitrate into a rare earth nitrate composite solution; adding the rare earth nitrate composite solution into the suspension, uniformly stirring, and heating and drying to obtain mixed powder; preparing a composite powder material: and carrying out two-step hydrogen reduction on the mixed powder to obtain the composite powder material. The multi-element composite rare earth electron emission material prepared by the method has no radioactive pollution, low oxygen content, low impurity content and uniform rare earth component distribution, and can be used for preparing tungsten electrodes for plasma spraying and argon arc welding with small burning loss and long service life.
Description
Technical field
The present invention relates to powder metallurgical technology, relate in particular to a kind of multiplex composite rare-earth electronic emission material and preparation method thereof.
Background technology
The advantages such as plasma spraying has that sprayed on material scope is wide, strong adaptability, coating binding force are strong, play an important role at aspects such as wear-resisting, thermal boundary, corrosion-resistant, insulation, radioresistance, catalysis.
Plasma spraying is to produce a direct-current arc between negative electrode and anode (nozzle), electric arc is ionized into high-temperature plasma the working gas heating importing, and spray from nozzle, form flame passes, the temperature of flame passes is very high, its central temperature can reach 32000K, and the temperature of jet expansion can reach 16000～20000K.Flame Flow Velocity can reach 1000～2000m/s at nozzle exit, and plasma spraying electric current generally exceedes 500A, higher than the conventional electric current 150-250A that uses of argon arc welding.Just because of the environment for use of this high temperature and high speed flame stream, large electric current makes the existing tungsten electrode life-span only have 40-50h.And the size of plasma tungsten electrode is larger, complex-shaped, therefore difficulty of processing is large, to having relatively high expectations of material.
Present stage, because applying working condition and scantling require harsh, the material selection of plasma gun tungsten electrode is still continued to use cerium tungsten or thorium tungsten both at home and abroad, there is following defect in the plasma gun tungsten electrode using at present: (1) thorium tungsten, containing radioactive element, works the mischief to environment and human body in processing, use procedure.(2) cerium tungsten electrode is on the low side service life.
Summary of the invention
The present invention can solve the deficiencies in the prior art, a kind of multiplex composite rare-earth electronic emission material and preparation method thereof is provided, a kind of no radioactivity pollute, impurity content and free oxygen content can be prepared low, rare earth composition is evenly distributed, and is applicable to preparation and meets the electrode material that electron work functon is low, scaling loss is little that plasma gun is applied.
For solving the problems of the technologies described above, the invention provides a kind of multiplex composite rare-earth electronic emission material, this material is to add the composite powder material that rare earth oxide is made in tungsten metallic matrix powder.
The present invention also provides a kind of preparation method of multiplex composite rare-earth electronic emission material, for the preparation of multiplex composite rare-earth electronic emission material of the present invention, comprises the following steps:
Take tungsten metallic matrix powder, rare earth oxide and nitrate as raw material;
Prepare mixed-powder: described tungsten metallic matrix powder is put into doping pot, add deionized water and stirring to obtain uniform suspension; Rare earth oxide and nitrate are configured to rare earth nitrades composite solution; Described rare earth nitrades composite solution is joined in described suspension and stirred, and heat drying obtains mixed-powder, and mixed-powder is crossed 80 mesh sieves;
Prepare composite powder material: described mixed-powder is carried out to two step hydrogen reductions: once reduction: described mixed-powder is reduced in hydrogen reducing furnace, the pure hydrogen protection with dew point lower than-30 ℃, reduction temperature is 550～700 ℃, the recovery time is 4～6 hours; Once after reduction, powder is crossed 80 mesh sieves, carries out secondary reduction, and secondary reduction adopts dew point to protect lower than the pure hydrogen of-30 ℃, and reduction temperature is 850～1000 ℃, and the recovery time is 4～6 hours, and after secondary reduction, powder is crossed 200 mesh sieves, obtains composite powder material.
Beneficial effect of the present invention is: this multiplex composite rare-earth electronic emission material no radioactivity pollute, impurity content and free oxygen content are low, rare earth composition is evenly distributed, and is applicable to prepare the electrode material that electron work functon is low, scaling loss is little of the application that meets plasma gun.
Accompanying drawing explanation
In order to be illustrated more clearly in the technical scheme of the embodiment of the present invention, below the accompanying drawing of required use during embodiment is described is briefly described, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, do not paying under the prerequisite of creative work, can also obtain other accompanying drawings according to these accompanying drawings.
The multiplex composite rare-earth electronic emission material preparation method schematic flow sheet that Fig. 1 provides for the embodiment of the present invention;
The electron scanning micrograph of the multiplex composite rare-earth electronic emission material that Fig. 2 provides for the embodiment of the present invention;
The multiplex composite rare-earth electronic emission material that Fig. 3 provides for the embodiment of the present invention can spectrogram.
The specific embodiment
Below the technical scheme in the embodiment of the present invention is clearly and completely described, obviously, described embodiment is only the present invention's part embodiment, rather than whole embodiment.Based on embodiments of the invention, those of ordinary skills, not making the every other embodiment obtaining under creative work prerequisite, belong to protection scope of the present invention.
The embodiment of the present invention provides a kind of multiplex composite rare-earth electronic emission material, and this material is to add the composite powder material that rare earth oxide is made in tungsten metallic matrix powder.
In above-mentioned multiplex composite rare-earth electronic emission material, tungsten metallic matrix powder is ammonium paratungstate APT powder, and particle mean size is 20～50um.
In above-mentioned multiplex composite rare-earth electronic emission material, the percentage that rare earth oxide accounts for composite powder material gross weight is 0.5～4.0%, rare earth oxide is lanthana, cerium oxide and scandium oxide, the percentage that wherein every kind of rare earth oxide accounts for composite powder material gross weight is 0.1～1.5%, as long as guarantee that total consumption of each rare earth oxide accounts for 0.5～4.0% of composite powder material gross weight.
The multiplex composite rare-earth electronic emission material of the embodiment of the present invention, be applicable to the raw material composite powder of the new multicomponent compound rare-earth electronic emission material of preparing plasma spray gun electrode and argon arc welding electrode, this composite powder material no radioactivity pollute, impurity content and free oxygen content are low, rare earth composition is evenly distributed, and is applicable to prepare the electrode material that electron work functon is low, scaling loss is little of the application that meets plasma gun.
The embodiment of the present invention also provides a kind of method of preparing above-mentioned multiplex composite rare-earth electronic emission material, as shown in Figure 1, comprises the following steps:
Take tungsten metallic matrix powder, rare earth oxide and nitrate as raw material;
Prepare mixed-powder: described tungsten metallic matrix powder is put into doping pot, add deionized water and stirring to obtain uniform suspension; Rare earth oxide and nitrate are configured to rare earth nitrades composite solution; Described rare earth nitrades composite solution is joined in described suspension and stirred, and heat drying obtains mixed-powder, and mixed-powder is crossed 80 mesh sieves;
Prepare composite powder material: described mixed-powder is carried out to two step hydrogen reductions: once reduction: described mixed-powder is reduced in hydrogen reducing furnace, the pure hydrogen protection with dew point lower than-30 ℃, reduction temperature is 550～700 ℃, the recovery time is 4～6 hours; Once after reduction, powder is crossed 80 mesh sieves, carries out secondary reduction, and secondary reduction adopts dew point to protect lower than the pure hydrogen of-30 ℃, and reduction temperature is 850～1000 ℃, and the recovery time is 4～6 hours, and after secondary reduction, powder is crossed 200 mesh sieves, obtains composite powder material.
The preparation method of above-mentioned multiplex composite rare-earth electronic emission material, rare earth oxide adopts lanthana (La
2o
3), cerium oxide (CeO
2) and scandium oxide (Sc
2o
3), described nitrate adopts lanthanum nitrate (La (NO
3)
36H
2o), cerous nitrate (Ce (NO
3)
36H
2and scandium nitrate (Sc (NO O)
3)
36H
2o), the consumption of described lanthanum nitrate, cerous nitrate and scandium nitrate takes by the content that contains lanthana, cerium oxide and scandium oxide in composite powder material after reduction respectively.
Below in conjunction with specific embodiment, the invention will be further described.
The multiplex composite rare-earth electronic emission material that the embodiment of the present invention provides, it is a kind of multielement rare earth tungsten electrode material, in the ammonium paratungstate powder that is 20～50um in particle mean size, to add rare earth oxide to make, rare earth oxide is lanthana, cerium oxide and three kinds of oxides of scandium oxide, and rare-earth oxidation tungsten total mass ratio in composite powder is 0.5～4.0%.
As shown in Figure 1, above-mentioned multiplex composite rare-earth electronic emission material is prepared by following steps:
(1) get the raw materials ready: the ammonium paratungstate powder that is 20～50um by granularity takes proportioning weight and pours in doping pot, adds deionized water and stirring to obtain uniform suspension; Be 0.5% according to lanthana content in tungsten powder after reduction, cerium oxide content is 1%, scandium oxide content is 1.5%, take lanthanum nitrate, cerous nitrate, scandium nitrate, be configured to rare earth nitrades composite solution, join in suspension and stir, with water-bath heat drying acquisition mixed-powder, 120 ℃ of heating-up temperatures, cross 80 mesh sieves by dried mixed-powder;
(2) once reduction: once reduce and carry out in hydrogen reducing furnace, every boat volume is 500cm
3, every boat charging 500g, reduction temperature is 550 ℃, the recovery time is 4 hours, the pure hydrogen protection with dew point lower than-30 ℃, the powder after reduction is crossed 80 mesh sieves;
(3) secondary reduction: secondary reduction carries out in hydrogen reducing furnace, will once reduce sieve after powder dress boat, every boat volume is 500cm
3, every boat charging 500g, reduction temperature is 850 ℃, the recovery time is 4 hours, the pure hydrogen protection with dew point lower than-30 ℃, the powder after reduction is crossed 200 mesh sieves.
The rare-earth tungsten electrode composite powder obtaining according to above-described embodiment is multiplex composite rare-earth electronic emission material, and as shown in table 1 below is the performance test results of above-described embodiment gained rare-earth tungsten electrode composite powder:
Table 1
Fig. 2,3 is depicted as SEM photo and the power spectrum result schematic diagram of the multiplex composite rare-earth electronic emission material raw material composite powder that the embodiment of the present invention makes, and can find out that rare earth composition is uniformly distributed in tungsten metallic matrix powder in figure.The multielement rare earth tungsten electrode material that multiplex composite rare-earth electronic emission material prepared by the present invention is made also can be applicable to the fields such as inert gas-shielded arc welding, plasma cutting, melting.
The above; only for the preferably specific embodiment of the present invention, but protection scope of the present invention is not limited to this, is anyly familiar with in technical scope that those skilled in the art disclose in the present invention; the variation that can expect easily or replacement, within all should being encompassed in protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claims.
Claims (7)
1. a multiplex composite rare-earth electronic emission material, is characterized in that, this material is to add the composite powder material that rare earth oxide is made in tungsten metallic matrix powder.
2. multiplex composite rare-earth electronic emission material according to claim 1, is characterized in that, described tungsten metallic matrix powder is ammonium paratungstate APT powder, and particle mean size is 20～50um.
3. multiplex composite rare-earth electronic emission material according to claim 1, is characterized in that, the percentage that described rare earth oxide accounts for described composite powder material gross weight is 0.5～4.0%.
4. according to the multiplex composite rare-earth electronic emission material described in claim 1,2 or 3, it is characterized in that, described rare earth oxide is lanthana, cerium oxide and scandium oxide, and the percentage that wherein every kind of rare earth oxide accounts for described composite powder material gross weight is 0.1～1.5%.
5. a preparation method for multiplex composite rare-earth electronic emission material, is characterized in that, for the preparation of the multiplex composite rare-earth electronic emission material described in claim 1 to 4 any one, comprises the following steps:
Take tungsten metallic matrix powder, rare earth oxide and nitrate as raw material;
Prepare mixed-powder: described tungsten metallic matrix powder is put into doping pot, add deionized water and stirring to obtain uniform suspension; Rare earth oxide and nitrate are configured to rare earth nitrades composite solution; Described rare earth nitrades composite solution is joined in described suspension and stirred, and heat drying obtains mixed-powder, and mixed-powder is crossed 80 mesh sieves;
Prepare composite powder material: described mixed-powder is carried out to two step hydrogen reductions: once reduction: described mixed-powder is reduced in hydrogen reducing furnace, the pure hydrogen protection with dew point lower than-30 ℃, reduction temperature is 550～700 ℃, the recovery time is 4～6 hours; Once after reduction, powder is crossed 80 mesh sieves, carries out secondary reduction, and secondary reduction adopts dew point to protect lower than the pure hydrogen of-30 ℃, and reduction temperature is 850～1000 ℃, and the recovery time is 4～6 hours, and after secondary reduction, powder is crossed 200 mesh sieves, obtains composite powder material.
6. the preparation method of multiplex composite rare-earth electronic emission material as claimed in claim 5, it is characterized in that, described rare earth oxide adopts lanthana, cerium oxide and scandium oxide, and the percentage that wherein every kind of rare earth oxide accounts for described composite powder material gross weight is 0.1～1.5%.
7. the preparation method of multiplex composite rare-earth electronic emission material as claimed in claim 5, is characterized in that, described in
Described nitrate adopts lanthanum nitrate, cerous nitrate and scandium nitrate, and the consumption of described lanthanum nitrate, cerous nitrate and scandium nitrate takes by the content that contains lanthana, cerium oxide and scandium oxide in composite powder material after reduction respectively.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105554995A (en) * | 2015-12-18 | 2016-05-04 | 中国科学院西安光学精密机械研究所 | High-density plasma generator |
| CN106834780A (en) * | 2017-01-20 | 2017-06-13 | 赣州有色冶金研究所 | A kind of W-REO alloys and preparation method thereof |
| CN107322002A (en) * | 2017-06-28 | 2017-11-07 | 合肥工业大学 | A kind of doped tungsten-based composite granule of rare earth oxide and preparation method thereof |
| CN107737951A (en) * | 2017-10-18 | 2018-02-27 | 北京科技大学 | A kind of preparation method of superfine crystal tungsten-based gas spark switch electrode |
| WO2021000447A1 (en) * | 2019-07-01 | 2021-01-07 | 北京工业大学 | Impregnation type scandium oxide doped rhenium-tungsten multi-phase mixed based dispenser cathode and preparation method |
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| FR2289290A1 (en) * | 1974-10-31 | 1976-05-28 | Siemens Ag | Tungsten welding electrodes for use with inert gas or plasma - where electrodes have long core contg. thoria |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105554995A (en) * | 2015-12-18 | 2016-05-04 | 中国科学院西安光学精密机械研究所 | High-density plasma generator |
| CN106834780A (en) * | 2017-01-20 | 2017-06-13 | 赣州有色冶金研究所 | A kind of W-REO alloys and preparation method thereof |
| CN107322002A (en) * | 2017-06-28 | 2017-11-07 | 合肥工业大学 | A kind of doped tungsten-based composite granule of rare earth oxide and preparation method thereof |
| CN107737951A (en) * | 2017-10-18 | 2018-02-27 | 北京科技大学 | A kind of preparation method of superfine crystal tungsten-based gas spark switch electrode |
| CN107737951B (en) * | 2017-10-18 | 2019-09-10 | 北京科技大学 | A kind of preparation method of superfine crystal tungsten-based gas spark switch electrode |
| WO2021000447A1 (en) * | 2019-07-01 | 2021-01-07 | 北京工业大学 | Impregnation type scandium oxide doped rhenium-tungsten multi-phase mixed based dispenser cathode and preparation method |
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