CN103769581B - 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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- CN103769581B CN103769581B CN201410059760.XA CN201410059760A CN103769581B CN 103769581 B CN103769581 B CN 103769581B CN 201410059760 A CN201410059760 A CN 201410059760A CN 103769581 B CN103769581 B CN 103769581B
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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, particularly relate to a kind of multiplex composite rare-earth electronic emission material and preparation method thereof.
Background technology
Plasma spraying has the advantages such as sprayed on material scope is wide, strong adaptability, coating binding force are strong, plays an important role in wear-resisting, thermal boundary, corrosion-resistant, insulation, radioresistance, catalysis etc.
Plasma spraying produces a direct-current arc between negative electrode and anode (nozzle), electric arc is ionized into high-temperature plasma the working gas heating imported, 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 more than 500A, uses electric current 150-250A higher than argon arc welding routine.Just because of the environment for use of this high temperature and high speed flame stream, big current, the existing tungsten electrode life-span is made only to have 40-50h.And the size of plasma tungsten electrode is larger, complex-shaped, therefore difficulty of processing is large, higher to the requirement of material.
Present stage, because applying working condition and scantling require harsh, the material selection of domestic and international plasma gun tungsten electrode still continues to use cerium tungsten or thorium tungsten, there is following defect in the plasma gun tungsten electrode of current use: (1) thorium tungsten, containing radioactive element, works the mischief to environment and human body in processing, use procedure.(2) Ce-W electrode is on the low side for 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 prepare the electrode material that electron work functon is low, scaling loss is little meeting plasma gun application.
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 in tungsten metallic matrix powder, add the composite powder material that rare earth oxide makes.
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:
With tungsten metallic matrix powder, rare earth oxide and nitrate for raw material;
Prepare mixed-powder: described tungsten metallic matrix powder is put into doping pot, add deionized water and stirring and obtain uniform suspension; Rare earth oxide and nitrate are configured to rare earth nitrades composite solution; Joined in described suspension by described rare earth nitrades composite solution and stir, heat drying obtains mixed-powder, and mixed-powder crosses 80 mesh sieves;
Prepare composite powder material: described mixed-powder is carried out two step hydrogen reductions: once reduce: reduced in hydrogen reducing furnace by described mixed-powder, with the pure hydrogen protection of dew point lower than-30 DEG C, reduction temperature is 550 ~ 700 DEG C, and the recovery time is 4 ~ 6 hours; Once after reduction, powder crosses 80 mesh sieves, carries out secondary reduction, and secondary reduction employing dew point is protected lower than the pure hydrogen of-30 DEG C, and reduction temperature is 850 ~ 1000 DEG C, and the recovery time is 4 ~ 6 hours, and after secondary reduction, powder crosses 200 mesh sieves, namely 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 meeting 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 used required in describing embodiment 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, under the prerequisite not paying creative work, other accompanying drawings can also be obtained 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 energy spectrogram of the multiplex composite rare-earth electronic emission material that Fig. 3 provides for the embodiment of the present invention.
Detailed description of the invention
Be clearly and completely described the technical scheme in the embodiment of the present invention below, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on embodiments of the invention, those of ordinary skill in the art, not making the every other embodiment obtained 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 in tungsten metallic matrix powder, add the composite powder material that rare earth oxide makes.
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 often kind of rare earth oxide accounts for composite powder material gross weight is 0.1 ~ 1.5%, as long as total ensure that the 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 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 meeting plasma gun.
The embodiment of the present invention also provides a kind of method preparing above-mentioned multiplex composite rare-earth electronic emission material, as shown in Figure 1, comprises the following steps:
With tungsten metallic matrix powder, rare earth oxide and nitrate for raw material;
Prepare mixed-powder: described tungsten metallic matrix powder is put into doping pot, add deionized water and stirring and obtain uniform suspension; Rare earth oxide and nitrate are configured to rare earth nitrades composite solution; Joined in described suspension by described rare earth nitrades composite solution and stir, heat drying obtains mixed-powder, and mixed-powder crosses 80 mesh sieves;
Prepare composite powder material: described mixed-powder is carried out two step hydrogen reductions: once reduce: reduced in hydrogen reducing furnace by described mixed-powder, with the pure hydrogen protection of dew point lower than-30 DEG C, reduction temperature is 550 ~ 700 DEG C, and the recovery time is 4 ~ 6 hours; Once after reduction, powder crosses 80 mesh sieves, carries out secondary reduction, and secondary reduction employing dew point is protected lower than the pure hydrogen of-30 DEG C, and reduction temperature is 850 ~ 1000 DEG C, and the recovery time is 4 ~ 6 hours, and after secondary reduction, powder crosses 200 mesh sieves, namely 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 containing 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, be add rare earth oxide in the ammonium paratungstate powder of 20 ~ 50um to make in particle mean size, rare earth oxide is lanthana, cerium oxide and scandium oxide three kinds of oxides, and the mass ratio total in composite powder of rare-earth oxidation tungsten 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: be that the ammonium paratungstate powder of 20 ~ 50um takes proportioning weight and pours in doping pot by granularity, add deionized water and stirring and obtain uniform suspension; According to after reduction in tungsten powder lanthana content be 0.5%, cerium-oxide contents 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, obtain mixed-powder with water-bath heat drying, heating-up temperature 120 DEG C, crosses 80 mesh sieves by dried mixed-powder;
(2) once reduce: once reduce and to carry out in hydrogen reducing furnace, every boat volume is 500cm
3, every boat charging 500g, reduction temperature is 550 DEG C, and the recovery time is 4 hours, and with the pure hydrogen protection of dew point lower than-30 DEG C, the powder after reduction crosses 80 mesh sieves;
(3) secondary reduction: secondary reduction carries out in hydrogen reducing furnace, the powder after sieving that will once reduce fills boat, and every boat volume is 500cm
3, every boat charging 500g, reduction temperature is 850 DEG C, and the recovery time is 4 hours, and with the pure hydrogen protection of dew point lower than-30 DEG C, the powder after reduction crosses 200 mesh sieves.
The rare-earth tungsten electrode composite powder obtained 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 obtains, 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 cut, melting.
The above; be only the present invention's preferably detailed description of the invention, but protection scope of the present invention is not limited thereto, is anyly familiar with those skilled in the art in the technical scope that the present invention discloses; the change that can expect easily or replacement, all should be encompassed within 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 (5)
1. a multiplex composite rare-earth electronic emission material, is characterized in that, this material is in tungsten metallic matrix powder, add the composite powder material that rare earth oxide makes; Described rare earth oxide is lanthana, cerium oxide and scandium oxide, and wherein lanthana content is 0.5%, and cerium-oxide contents is 1%, and scandium oxide content is 1.5%.
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. 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 any one of claims 1 to 3, comprises the following steps:
With tungsten metallic matrix powder, rare earth oxide and nitrate for raw material; Described rare earth oxide is lanthana, cerium oxide and scandium oxide, and wherein lanthana content is 0.5%, and cerium-oxide contents is 1%, and scandium oxide content is 1.5%;
Prepare mixed-powder: described tungsten metallic matrix powder is put into doping pot, add deionized water and stirring and obtain uniform suspension; Rare earth oxide and nitrate are configured to rare earth nitrades composite solution; Joined in described suspension by described rare earth nitrades composite solution and stir, heat drying obtains mixed-powder, and mixed-powder crosses 80 mesh sieves;
Prepare composite powder material: the mixed-powder after sieving is carried out two step hydrogen reductions: once reduce: reduced in hydrogen reducing furnace by described mixed-powder, with the pure hydrogen protection of dew point lower than-30 DEG C, reduction temperature is 550 ~ 700 DEG C, and the recovery time is 4 ~ 6 hours; Once after reduction, powder crosses 80 mesh sieves, carries out secondary reduction, and secondary reduction employing dew point is protected lower than the pure hydrogen of-30 DEG C, and reduction temperature is 850 ~ 1000 DEG C, and the recovery time is 4 ~ 6 hours, and after secondary reduction, powder crosses 200 mesh sieves, namely obtains composite powder material.
5. the preparation method of multiplex composite rare-earth electronic emission material as claimed in claim 4, it is characterized in that, 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 containing lanthana, cerium oxide and scandium oxide in composite powder material after reduction respectively.
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| CN105554995B (en) * | 2015-12-18 | 2018-12-14 | 中国科学院西安光学精密机械研究所 | High Density Plasma Generator |
| CN106834780B (en) * | 2017-01-20 | 2018-09-25 | 赣州有色冶金研究所 | A kind of W-REO alloys and preparation method thereof |
| CN107322002B (en) * | 2017-06-28 | 2020-01-17 | 合肥工业大学 | Rare earth oxide doped tungsten-based composite powder and preparation method thereof |
| 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 |
| CN110303165B (en) * | 2019-07-01 | 2020-11-20 | 北京工业大学 | Impregnated scandium oxide doped rhenium-tungsten multiphase mixed base diffusion cathode and preparation method thereof |
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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 |
| CN1041556A (en) * | 1988-10-04 | 1990-04-25 | 冶金工业部包头稀土研究院 | Rare-earth tungsten electrode material and production method thereof |
| CN1586797A (en) * | 2004-09-30 | 2005-03-02 | 北京矿冶研究总院 | Preparation method of multicomponent composite rare earth-tungsten electrode material |
| CN102000923A (en) * | 2010-09-20 | 2011-04-06 | 天津市春风钨业有限公司 | Multi-element composite rare earth tungsten electrode material and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| CN1041556A (en) * | 1988-10-04 | 1990-04-25 | 冶金工业部包头稀土研究院 | Rare-earth tungsten electrode material and production method thereof |
| CN1586797A (en) * | 2004-09-30 | 2005-03-02 | 北京矿冶研究总院 | Preparation method of multicomponent composite rare earth-tungsten electrode material |
| CN102000923A (en) * | 2010-09-20 | 2011-04-06 | 天津市春风钨业有限公司 | Multi-element composite rare earth tungsten electrode material and preparation method thereof |
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