CN1089813C - Electron valve cathode material and preparation method thereof - Google Patents
Electron valve cathode material and preparation method thereof Download PDFInfo
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- CN1089813C CN1089813C CN99109750A CN99109750A CN1089813C CN 1089813 C CN1089813 C CN 1089813C CN 99109750 A CN99109750 A CN 99109750A CN 99109750 A CN99109750 A CN 99109750A CN 1089813 C CN1089813 C CN 1089813C
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- Prior art keywords
- carbonization
- cathode material
- rare earth
- electron valve
- molybdenum
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- 239000010406 cathode material Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000003763 carbonization Methods 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 32
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 22
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 14
- 239000011733 molybdenum Substances 0.000 claims abstract description 14
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 11
- 230000004913 activation Effects 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 2
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 8
- 150000002910 rare earth metals Chemical class 0.000 abstract description 8
- 229910003178 Mo2C Inorganic materials 0.000 abstract 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 abstract 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 abstract 1
- 238000000137 annealing Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 238000001354 calcination Methods 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 238000009413 insulation Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000005498 polishing Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000005245 sintering Methods 0.000 description 6
- 238000010561 standard procedure Methods 0.000 description 6
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical class [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 4
- BXJPTTGFESFXJU-UHFFFAOYSA-N yttrium(3+);trinitrate Chemical class [Y+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O BXJPTTGFESFXJU-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- 238000009954 braiding Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000003904 radioactive pollution Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- WLTSUBTXQJEURO-UHFFFAOYSA-N thorium tungsten Chemical compound [W].[Th] WLTSUBTXQJEURO-UHFFFAOYSA-N 0.000 description 1
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Abstract
The present invention relates to a cathode material of an electron valve and a preparation method thereof. The cathode material belongs to the technical field of rare earth metal-molybdenum materials. The cathode material of the electron valve has one or two kinds of rare earth oxide in La2O3 and Y2O3, wherein the rare earth oxide accounts for 3.0 to 5.0% of the total weight of the molybdenum. In a one-step carbonization process adopted by the preparation method of the cathode material of the electron valve, the carbonization temperature is controlled between 1300 and 1500 DEG C, the carbonization lasts 8 minutes, the benzene pressure during the carbonization is between 8.5 and 9.5 Pa, the carbonization degree is between 5% and 10%, a Mo2C layer is formed on the surface of thread materials after the carbonization, and the grain orientation is perpendicular to the surface of the thread materials. The cathode material of the electron valve prepared by the method t has the advantages of low operation temperature and long service life.
Description
A kind of electron valve cathode material and preparation method thereof belongs to rare earth metal-Mo technical field.
At present, the thoriated-tungsten cathode (Th-W) of the thoriatde-tungsten wire braiding that remains T﹠B that the cathode material of high power valve mainly uses, the thoriated-tungsten cathode launch stability is good, but because its working temperature height (more than 1800 ℃), energy consumption are big, easily influence its working reliability, even more serious is the Th-W material preparation, use and discarded process in exist radioactive pollution, and fragility is big, lumber recovery is low, so it is not the ideal cathode material.
Both at home and abroad to La
2O
3-Mo (La-Mo) material itself is studied, and mentioning the La-Mo material in the Japanese Patent (JP59-179754) is a kind of structured material, also is a kind of thermionic emission materials, but does not have emission stability and lifetime data in this document.Domestic once had 1-2 unit to study at the mid-80, but do not see further report because of launching the short reasons such as (tens hours) of instability, life-span.Therefore also to exist transmitter current at present little for the La-Mo material, and emission is unstable, and the short problem that hinders practicability that waits of life-span can't be used on practical triode.
The objective of the invention is to overcome the defective that exists in the above-mentioned prior art, low, the "dead" pollution of a kind of working temperature is provided, launches electron valve cathode material stable, that the life-span is long.
Electron valve cathode material proposed by the invention is characterized in that: it contains La
2O
3And Y
2O
3In one or both rare earth oxides, the gross weight that rare earth oxide accounts for molybdenum is 3.0～5.0%, surplus is Mo.
In above-mentioned electron valve cathode material, the gross weight that rare earth oxide accounts for molybdenum is the best with 4.0%.
The preparation method of electron valve cathode material proposed by the invention, comprise a material cleaning, negative electrode coiling, carbonization, shelve, exhaust activation, negative electrode be seasoned, it is characterized in that: adopted carbonization technique one time, and (1) carbonization temperature is controlled between 1300～1500 ℃ in carbonization technique; (2) carbonization time is 8 minutes; (3) during carbonization benzene to press be 8.5～9.5Pa; (4) degree of carbonisation is 5～10%; (5) form Mo on silk material surface after the carbonization
2The C layer, grain orientation and silk material Surface Vertical.
Description of drawings: Fig. 1: 6T51 type electron tube transmitter current and the time chart made with cathode material of the present invention.
Embodiment:
Example 1,1062.4 gram lanthanum nitrates are water-soluble is added to 10000 gram powdery MoO
2In (La wherein
2O
3The weight ratio that accounts for molybdenum is 4.0%), the MoO after mixing
2Powder is reduced into doping La then 550 ℃ of following calcinations 2 hours in 700～1000 ℃ multi-stage type hydrogen furnace
2O
3The rare earth molybdenum powder, through die mould, sintering, swage, Mo-La that stretch process becomes diameter phi 1.04mm
2O
3Silk material (being called for short ML-1#).After removing surperficial aquadag or oxide skin with electrolytic polishing method, turn to the 6T51 negative electrode, annealing process: 9V * 60 second → 11V * 60 second → 0V → 12V * 10 second, carbonization technique: 1400 ℃ of carbonization temperatures, voltage 5V insulation 8 minutes, benzene is pressed 8.5Pa, and degree of carbonisation is 5.7%, makes 6T51 type electron tube through operations such as tubulature, exhaust activation, negative electrode are seasoned then.Measure pulse emission and life parameter with standard method, see Table 1.
Example 2,1062.4 gram lanthanum nitrates are water-soluble is added to 10000 gram powdery MoO
2In (La wherein
2O
3The weight ratio that accounts for molybdenum is 4.0%), the MoO after mixing
2Powder is reduced into doping La then 550 ℃ of following calcinations 2 hours in 700～1000 ℃ multi-stage type hydrogen furnace
2O
3The rare earth molybdenum powder, through die mould, sintering, swage, Mo-La that stretch process becomes diameter phi 1.04mm
2O
3Silk material (being called for short ML-2#).After removing surperficial aquadag or oxide skin with electrolytic polishing method, turn to the 6T51 negative electrode, annealing process: 9V * 60 second → 11V * 60 second → 0V → 12V * 10 second, carbonization technique: 1500 ℃ of carbonization temperatures, voltage 5.5V insulation 8 minutes, benzene is pressed 9.5Pa, and degree of carbonisation is 9.8%, makes 6T51 type electron tube through operations such as tubulature, exhaust activation, negative electrode are seasoned then.Measure pulse emission and life parameter with standard method, see Table 1.
Example 3,1356.9 gram Yttrium trinitrates are water-soluble is added to 10000 gram powdery MoO
2In (Y wherein
2O
3The weight ratio that accounts for molybdenum is 4.0%), the MoO after mixing
2Powder is reduced into doping Y then 550 ℃ of following calcinations 2 hours in 700～1000 ℃ multi-stage type hydrogen furnace
2O
3The rare earth molybdenum powder, through die mould, sintering, swage, Mo-Y that stretch process becomes diameter phi 1.04mm
2O
3Silk material (being called for short MY-1#).After removing surperficial aquadag or oxide skin with electrolytic polishing method, turn to the 6T51 negative electrode, annealing process: 9V * 60 second → 11V * 60 second → 0V → 12V * 10 second, carbonization technique: 1400 ℃ of carbonization temperatures, voltage 5V insulation 8 minutes, benzene is pressed 8.5Pa, and degree of carbonisation is 6.8%, makes 6T51 type electron tube through operations such as tubulature, exhaust activation, negative electrode are seasoned then.Measure pulse emission and life parameter with standard method, see Table 1.
Example 4,1356.9 gram Yttrium trinitrates are water-soluble is added to 10000 gram powdery MoO
2In (Y wherein
2O
3The weight ratio that accounts for molybdenum is 4.0%), the MoO after mixing
2Powder is reduced into doping Y then 550 ℃ of following calcinations 2 hours in 700～1000 ℃ multi-stage type hydrogen furnace
2O
3The rare earth molybdenum powder, through die mould, sintering, swage, Mo-Y that stretch process becomes diameter phi 1.04mm
2O
3Silk material (being called for short MY-2#).After removing surperficial aquadag or oxide skin with electrolytic polishing method, turn to the 6T51 negative electrode, annealing process: 9V * 60 second → 11V * 60 second → 0V → 12V * 10 second, carbonization technique: 1500 ℃ of carbonization temperatures, voltage 5.5V insulation 8 minutes, benzene is pressed 9.5Pa, and degree of carbonisation is 9.5%, makes 6T51 type electron tube through operations such as tubulature, exhaust activation, negative electrode are seasoned then.Measure pulse emission and life parameter with standard method, see Table 1.
Example 5,398.4 gram lanthanum nitrates and 508.8 gram Yttrium trinitrates are water-soluble respectively is added to 10000 gram powdery MoO
2In (La wherein
2O
3The weight ratio that accounts for molybdenum is 2.0%, Y
2O
3The weight ratio that accounts for molybdenum is 2.0%), the MoO after mixing
2Powder is reduced into doping La then 550 ℃ of following calcinations 2 hours in 700～1000 ℃ multi-stage type hydrogen furnace
2O
3And Y
2O
3The compound rare-earth molybdenum powder, through die mould, sintering, swage, Mo-La that stretch process becomes diameter phi 1.04mm
2O
3-Y
2O
3Silk material (being called for short MLY-1#).After removing surperficial aquadag or oxide skin with electrolytic polishing method, turn to the 6T51 negative electrode, annealing process: 9V * 60 second → 11V * 60 second → 0V → 12V * 10 second, carbonization technique: 1400 ℃ of carbonization temperatures, voltage 5V insulation 8 minutes, benzene is pressed 8.5Pa, and degree of carbonisation is 6.0%, makes 6T51 type electron tube through operations such as tubulature, exhaust activation, negative electrode are seasoned then.Measure pulse emission and life parameter with standard method, see Table 1.
Example 6,398.4 gram lanthanum nitrates and 508.8 gram Yttrium trinitrates are water-soluble respectively is added to 10000 gram powdery MoO
2In (La wherein
2O
3The weight ratio that accounts for molybdenum is 2.0%, Y
2O
3The weight ratio that accounts for molybdenum is 2.0%), the MoO after mixing
2Powder is reduced into doping La then 550 ℃ of following calcinations 2 hours in 700～1000 ℃ multi-stage type hydrogen furnace
2O
3And Y
2O
3The compound rare-earth molybdenum powder, through die mould, sintering, swage, Mo-La that stretch process becomes diameter phi 1.04mm
2O
3-Y
2O
3Silk material (being called for short MLY-2#).After removing surperficial aquadag or oxide skin with electrolytic polishing method, turn to the 6T51 negative electrode, annealing process: 9V * 60 second → 11V * 60 second → 0V → 12V * 10 second, carbonization technique: 1500 ℃ of carbonization temperatures, voltage 5.5V insulation 8 minutes, benzene is pressed 9.5Pa, and degree of carbonisation is 10%, makes 6T51 type electron tube through operations such as tubulature, exhaust activation, negative electrode are seasoned then.Measure pulse emission and life parameter with standard method, see Table 1.
According to test, when total amount of the rare earth oxide less than 2.0% the time, the emission of cathode electric current is little; Total amount of the rare earth oxide is greater than 5.0% o'clock, silk material poor processability, and splitting easily when having only total amount of the rare earth oxide between 3.0～5.0%, just has good processing properties and emitting performance.
According to test, when the cathode carbonization temperature was lower than 1300 ℃, degree of carbonisation was too little, launched also little; When the cathode carbonization temperature was higher than 1500 ℃, oxide compound volatilized seriously during carbonization, and carburization zone and matrix bond are poor, and cathode life is short, when therefore having only carbonization temperature to be controlled between 1300～1500 ℃, just can obtain ideal degree of carbonisation and life-span.In addition, because preparation W-ThO
2The cathode material carbonization temperature must be controlled at more than 1800 ℃, thereby adopts present method can reduce carbonization temperature greatly.
Cathode for electron tube proposed by the invention, working temperature is low, the life-span is long, and emission reaches 800mA under the 130W heating power, and heating power descends 40% than same model thorium tungsten electron tube, stable emission 1200 hours.
See Fig. 1, as can be seen from Figure 1, highly stable with the 6T51 type electron tube transmitter current that cathode material of the present invention is made.
Table 1 triode tubulature cathod filament processing parameter
| Negative electrode | Annealing | Carbonization | Degree of carbonisation (%) | |||
| Voltage (V) | Time (second) | Voltage (V) | Time (branch) | Benzene is pressed (Pa) | ||
| ML-1# | 9 11 12 | 60 60 10 | 5 | 8 | 8.5 | 5.7 |
| ML-2# | 9 11 12 | 60 60 10 | 5.5 | 8 | 9.5 | 9.8 |
| MY-1# | 9 11 12 | 60 60 10 | 5 | 8 | 8.5 | 6.8 |
| MY-2# | 9 11 12 | 60 60 10 | 5.5 | 8 | 9.5 | 9.5 |
| MLY- 1# | 9 11 12 | 60 60 10 | 5 | 8 | 8.5 | 6.0 |
| MLY- 2# | 9 11 12 | 60 60 10 | 5.5 | 8 | 9.5 | 10.0 |
Claims (3)
1, a kind of electron valve cathode material, it is characterized in that: it contains La
2O
3And Y
2O
3In one or both rare earth oxides, the gross weight that rare earth oxide accounts for molybdenum is 3.0～5.0%, surplus is Mo.
2, electron valve cathode material according to claim 1 is characterized in that: the gross weight that rare earth oxide accounts for molybdenum is 4.0%.
3, the preparation method of the described electron valve cathode material of a kind of claim 1 comprises a material cleaning, negative electrode coiling, carbonization, shelves, exhaust activation, negative electrode be seasoned, it is characterized in that: adopted carbonization technique one time, and in carbonization technique,
(1) carbonization temperature is controlled between 1300～1500 ℃;
(2) carbonization time is 8 minutes;
(3) during carbonization benzene to press be 8.5～9.5Pa;
(4) degree of carbonisation is 5～10%;
(5) form Mo on silk material surface after the carbonization
2The C layer, grain orientation and silk material Surface Vertical.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99109750A CN1089813C (en) | 1999-07-12 | 1999-07-12 | Electron valve cathode material and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99109750A CN1089813C (en) | 1999-07-12 | 1999-07-12 | Electron valve cathode material and preparation method thereof |
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|---|---|
| CN1240235A CN1240235A (en) | 2000-01-05 |
| CN1089813C true CN1089813C (en) | 2002-08-28 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103700557B (en) * | 2013-12-24 | 2016-03-30 | 北京工业大学 | A kind of carbonization rare-earth oxidation lutetium doping molybdenum cathode material and preparation method thereof |
| CN106328468B (en) * | 2016-08-21 | 2018-04-17 | 北京工业大学 | The preparation method of magnetron La2O3 doping Mo cathode materials |
| CN106206215B (en) * | 2016-08-21 | 2018-03-09 | 北京工业大学 | A kind of compound La of binary2O3、Ta2O5Doping molybdenum cathode material and preparation method thereof |
| CN106206216B (en) * | 2016-08-26 | 2018-04-17 | 北京工业大学 | Be carbonized La2O3 and the composite mixed Mo cathode materials of Lu2O3 and preparation method thereof |
| CN107507747A (en) * | 2017-08-17 | 2017-12-22 | 太仓劲松智能化电子科技有限公司 | Vacuum electronic tube preparation method |
| CN108376638B (en) * | 2018-02-01 | 2020-01-31 | 深圳凯世光研股份有限公司 | kinds of thorium tungsten electrodes and method for permeating ditungsten carbide layer on surfaces of thorium tungsten electrodes |
| CN115954245A (en) * | 2022-11-30 | 2023-04-11 | 朱惠冲 | Processing technology of satellite communication high-frequency electromagnetic cathode assembly |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1195707A (en) * | 1997-05-08 | 1998-10-14 | 北京工业大学 | Lanthanum oxide molydenum foil strip and its manufacturing method |
-
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1195707A (en) * | 1997-05-08 | 1998-10-14 | 北京工业大学 | Lanthanum oxide molydenum foil strip and its manufacturing method |
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