CN1176480C - High-current density electronic emission body rareearth-Sc-W based material and mfg. method thereof - Google Patents
High-current density electronic emission body rareearth-Sc-W based material and mfg. method thereof Download PDFInfo
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- CN1176480C CN1176480C CNB021313458A CN02131345A CN1176480C CN 1176480 C CN1176480 C CN 1176480C CN B021313458 A CNB021313458 A CN B021313458A CN 02131345 A CN02131345 A CN 02131345A CN 1176480 C CN1176480 C CN 1176480C
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Abstract
The present invention relates to electronic emitter materials of a rare earth scandium and tungsten base with high-current density and a preparation method of the electronic emitter materials, which belongs to the technical field of cathode materials of rare earth refractory metal. The materials of the present invention are characterized in that the materials contain scandium oxides, rhenium and tungsten, wherein the scandium oxides account for 1 to 10% of the weight percent of the electronic emitter materials, the rhenium accounts for 0 to 5%, and the rest is the tungsten. The preparation method provided by the present invention is characterized in that the method comprises the following steps that 1 to 10% of scandium oxides are added in the form of scandium nitrate water solution in blue tungsten, 0 to 5 % of rhenium is added in the form of ammonium rhenate water solution at the same time, the scandium oxides and the rhenium are reduced for 0.5 to 1.5 hours at the temperature of 500 to 650 DEG C in a hydrogen gas atmosphere, reduction and temperature preservation are carried out for 1 to 3 hours at the temperature of 800 to 1000 DEG C, and tungsten powder doped with the scandium oxides is obtained; the tungsten powder is prepared into a sintered body in a conventional powder metallurgy method; aluminate is infused, and the electronic emitter materials are made after ultrasonic cleaning and anneal. The electronic emitter materials of the present invention have uniform emission performance, high-temperature resisting and ionic bombardment resisting capabilities are improved, and the preparation method of the present invention has good technological repeatability.
Description
One, technical field
A kind of rareearth-Sc-W based high electric current density electron emitter material and preparation method thereof belongs to rare earth refractory metal cathode material technical field.
Two, background technology
Electron emitter is the heart of vacuum electron device.Vacuum display device and microwave device occupy critical role in information industry and military engineering.The vacuum display device that comprises picture tube and display tube develops rapidly in recent years.Along with this class device to the development of large-screen and high definition, more and more higher to the emission and the requirement in life-span that are applied to electron emitter wherein, with from early stage 0.5A/cm
2To 2A/cm
2, 4A/cm
2And even higher current density development.Traditional oxide coated cathode can not satisfy this requirement fully, and the new oxide negative electrode that development in recent years is got up is at 2A/cm
2Also be subjected to serious restriction when more than using.Unique and the irreplaceable effect of vacuum microwave electronic device in military and space technology confirmed by the development of modern war and aerospace industry.Along with operating frequency is made progress to millimere-wave band, the device dimension microminiaturization, target hangs down working temperature, high current density and long-life to require order to be becoming tight urgent.
Scandium series cathode has been subjected to attracting attention widely as the sub-emitter of a kind of desirable large-current electric, is considered to the representative of negative electrode of future generation.Up to now, the adding method of electron emitter middle rare earth element is mainly and adds scandium oxide or thin film deposition in aluminate.This type of electron emitter mostly faces the problem of following general character:
(1) distribution of the rare earth Sc after the interpolation or its oxide is inhomogeneous, thereby causes the appearance of the inhomogeneous and unusual Schottky effect of emission.
(2) diffusion of rare earth Sc and oxide thereof is bad, makes to replenish difficulty, and high temperature resistant, anti-ion bombardment poor performance influences the raising of cathode life.
(3) process repeatability is bad.
The existence of these problems has limited the development and the application of this electron-like emitter, thereby is one of focus of research in the field of world's electron emitter.The research contents that the present invention carries out is not seen the home and abroad report as yet.
Three, summary of the invention
Above problem at the prior art existence, a kind of rareearth-Sc-W based high electric current density electron emitter material provided by the present invention, it is characterized in that: it contains scandium oxide, rhenium and tungsten, wherein to account for this electron emitter material percentage by weight be 1-10% to scandium oxide, rhenium accounts for 1-5%, and all the other are tungsten.
A kind of rareearth-Sc-W based high electric current density electron emitter material preparation method provided by the present invention is characterized in that it may further comprise the steps:
Step 1: in blue tungsten, the scandium oxide that adds 1-10% with scandium nitrate aqueous solution form, the rhenium that adds 1-5% with the form of the rehenic acid aqueous ammonium mixture of scandium oxide that obtains mixing simultaneously, percentage wherein is the percentage by weight that accounts in the rareearth-Sc-W based high electric current density electron emitter material of end product;
Step 2: in hydrogen atmosphere, said mixture was reduced 0.5-1.5 hour down at 500-650 ℃; 800-1000 ℃ of down reduction insulation 1-3 hour, the tungsten powder of the scandium oxide that obtains mixing;
Step 3: adopt conventional powder metallurgy process to prepare the rareearth-Sc-W sintered body above-mentioned tungsten powder;
Step 4:, after ultrasonic waves for cleaning and the annealing, make electron emitter material with above-mentioned rareearth-Sc-W sintered body dipping aluminate.
The performance of rareearth-Sc-W based high electric current density electron emitter material provided by the present invention is: in this electron emitter material, the distribution of scandium oxide is very even; Equally distributed scandium oxide covers the surface of tungsten particle as film, stays but that enough holes freely spread for barium and scandium adds to the surface of negative electrode, thereby has improved high temperature resistant, the anti-ion bombardment ability of negative electrode.Though uniformity makes moderate progress in the thin film deposition processes, it is bad that thicknesses of layers is difficult to control repeatability, and preparation method's repeatability provided by the invention is good relatively.
Closely measuring the pulse heat emission in the planar diode structure, to see Table 1 as the current density results that negative electrode records embodiment 1-4 under 850 ℃ and 950 ℃ of working temperatures, visible electron emitter material provided by the invention has good emitting performance, and (general electron emitter material current density reaches several A.cm under identical working temperature
-2Just can satisfy instructions for use).With the original position auger analysis studied the heating and ion bombardment under surface composition and variation, the original position auger analysis of embodiment 1-4 the results are shown in Figure 1-4, the content of scandium is not found obvious variation, thereby rareearth-Sc-W based high electric current density electron emitter material provided by the invention has good high temperature resistance and anti-ion bombardment ability.
Four, description of drawings
Surface composition and the change curve of Fig. 1: embodiment 1 under heating and ion bombardment;
Surface composition and the change curve of Fig. 2: embodiment 2 under heating and ion bombardment;
Surface composition and the change curve of Fig. 3: embodiment 3 under heating and ion bombardment;
Surface composition and the change curve of Fig. 4: embodiment 4 under heating and ion bombardment.
Five, embodiment
Example 1,10.05 gram scandium nitrates are soluble in water, join in the blue tungsten of 120.64 gram powderies (wherein scandium oxide account for the rareearth-Sc-W based high electric current density electron emitter material total weight of end product 3%), in the multistage hydrogen furnace, 650 ℃ were reduced 1 hour, 900 ℃ of reduction insulations 2 hours, the tungsten powder of the scandium oxide that obtains mixing; Above-mentioned doping scandium oxide tungsten powder is pressed into the thin slice sample of Ф 3.5 * 1mm on hydraulic press, pressing pressure is 350Mpa/cm
2, in the tungsten silk screen stove, under hydrogen atmosphere, 1750 ℃, carry out sintering processes, preparation rareearth-Sc-W sintered body.With above-mentioned sintered body dipping aluminate, after ultrasonic waves for cleaning and the annealing, with molybdenum sleeve laser welding, make electron emitter material subsequently.
Example 2, with 10.05 gram scandium nitrates and 1.441 gram rehenic acid ammoniums, water-soluble respectively, join in the blue tungsten of 119.39 gram powderies that (wherein scandium oxide accounts for 3% of total weight in the rareearth-Sc-W based high electric current density electron emitter material of end product, rhenium accounts for 1%), in the multistage hydrogen furnace, 500 ℃ of reduction 1 hour, 800 ℃ of reduction insulations 3 hours, the powder of obtain mixing scandium oxide and rhenium; Above-mentioned tungsten powder is pressed into the thin slice sample of Ф 3.5 * 1mm on hydraulic press, pressing pressure is 350Mpa/cm
2, in the tungsten silk screen stove, under hydrogen atmosphere, 1400 ℃, carry out sintering processes, preparation rareearth-Sc-W sintered body.With above-mentioned sintered body dipping aluminate, after ultrasonic waves for cleaning and the annealing, with molybdenum sleeve laser welding, make electron emitter material subsequently.
Example 3, with 33.50 gram scandium nitrates and 4.323 gram rehenic acid ammoniums, water-soluble respectively, join in the blue tungsten of 108.20 gram powderies that (wherein scandium oxide accounts for 10% of total weight in the rareearth-Sc-W based high electric current density electron emitter material of end product, rhenium accounts for 3%), in the multistage hydrogen furnace, 650 ℃ were reduced 1.5 hours, 900 ℃ of reduction are incubated 2 hours, obtain mixing scandium oxide and rhenium are pressed into the thin slice sample of Ф 3.5 * 1mm with this tungsten powder on hydraulic press, pressing pressure is 350Mpa/cm
2, in the tungsten silk screen stove, under hydrogen atmosphere, 1400 ℃, carry out sintering processes, preparation rareearth-Sc-W sintered body.With above-mentioned sintered body dipping aluminate, after ultrasonic waves for cleaning and the annealing, with molybdenum sleeve laser welding, make electron emitter material subsequently.
Example 4, with 3.35 gram scandium nitrates and 7.205 gram rehenic acid ammoniums, water-soluble respectively, join in the blue tungsten of 116.91 gram powderies that (wherein scandium oxide accounts for 1% of total weight in the rareearth-Sc-W based high electric current density electron emitter material of end product, rhenium accounts for 5%), in the multistage hydrogen furnace, 600 ℃ were reduced 0.5 hour, 1000 ℃ of reduction are incubated 1 hour, obtain the mixing tungsten powder of scandium oxide and rhenium is pressed into the thin slice sample of Ф 3.5 * 1mm with this tungsten powder on hydraulic press, pressing pressure is 350Mpa/cm
2, in the tungsten silk screen stove, under hydrogen atmosphere, 1300 ℃, carry out sintering processes, preparation rareearth-Sc-W sintered body.With above-mentioned sintered body proofing aluminate, after ultrasonic waves for cleaning and the annealing, with molybdenum sleeve laser welding, make electron emitter material subsequently.
Table 1
Claims (2)
1, a kind of rareearth-Sc-W based high electric current density electron emitter material, it is characterized in that: it contains scandium oxide, rhenium and tungsten, and wherein to account for this electron emitter material percentage by weight be 1-10% to scandium oxide, and rhenium accounts for 1-5%, and all the other are tungsten.
2, a kind of rareearth-Sc-W based high electric current density electron emitter material preparation method is characterized in that it may further comprise the steps:
Step 1: in blue tungsten, the scandium oxide that adds 1-10% with scandium nitrate aqueous solution form, the rhenium that adds 1-5% with the form of the rehenic acid aqueous ammonium mixture of scandium oxide that obtains mixing simultaneously, percentage wherein is the percentage by weight that accounts in the rareearth-Sc-W based high electric current density electron emitter material of end product;
Step 2: in hydrogen atmosphere, said mixture was reduced 0.5-1.5 hour down at 500-650 ℃; 800-1000 ℃ of down reduction insulation 1-3 hour, the tungsten powder of the scandium oxide that obtains mixing;
Step 3: adopt conventional powder metallurgy process to prepare the rareearth-Sc-W sintered body above-mentioned tungsten powder;
Step 4:, after ultrasonic waves for cleaning and the annealing, make electron emitter material with above-mentioned rareearth-Sc-W sintered body dipping aluminate.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101834106B (en) * | 2010-05-12 | 2012-10-24 | 安徽华东光电技术研究所 | Tungsten-based impregnated cathode and preparation method thereof |
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| CN1304152C (en) * | 2005-03-14 | 2007-03-14 | 北京工业大学 | Production for powdery diffused cathode base material containing scandium |
| CN102259189A (en) * | 2011-07-28 | 2011-11-30 | 北京科技大学 | Preparation method of porous cathode substrate |
| CN103165361B (en) * | 2013-03-13 | 2015-11-25 | 清华大学深圳研究生院 | A kind of preparation method containing cesium compound negative electrode and this negative electrode |
| CN104299869B (en) * | 2014-09-26 | 2017-01-11 | 北京工业大学 | Impregnated Re3W-Sc2O3 mixed base cathode material and preparation method thereof |
| CN105331840B (en) * | 2015-10-20 | 2017-06-13 | 安泰科技股份有限公司 | A kind of tungsten base electrode material and preparation method thereof |
| CN105803285B (en) * | 2016-03-21 | 2017-08-11 | 合肥工业大学 | A kind of Ultra-fine Grained Sc2O3Adulterate W based composites and preparation method thereof |
| 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 |
| CN110142415A (en) * | 2019-07-01 | 2019-08-20 | 北京工业大学 | The oxide-doped more alloy phase tungsten-rhenium alloy powder of one kind and preparation method |
| CN111041317A (en) * | 2019-12-19 | 2020-04-21 | 厦门钨业股份有限公司 | Micro-nano composite reinforced tungsten alloy material and preparation method thereof |
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| CN101834106B (en) * | 2010-05-12 | 2012-10-24 | 安徽华东光电技术研究所 | Tungsten-based impregnated cathode and preparation method thereof |
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