CN105679624B - A kind of electronic emission material of resistance to bombardment and preparation method thereof - Google Patents
A kind of electronic emission material of resistance to bombardment and preparation method thereof Download PDFInfo
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- CN105679624B CN105679624B CN201610120082.2A CN201610120082A CN105679624B CN 105679624 B CN105679624 B CN 105679624B CN 201610120082 A CN201610120082 A CN 201610120082A CN 105679624 B CN105679624 B CN 105679624B
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- 239000000463 material Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000000498 ball milling Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 19
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium(III) oxide Inorganic materials O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 claims description 12
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 238000009835 boiling Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000001556 precipitation Methods 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 238000003828 vacuum filtration Methods 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
- 229910000018 strontium carbonate Inorganic materials 0.000 claims 1
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 claims 1
- 229910002651 NO3 Inorganic materials 0.000 abstract description 11
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract description 10
- 229910001404 rare earth metal oxide Inorganic materials 0.000 abstract description 7
- 239000002245 particle Substances 0.000 abstract description 5
- 238000002425 crystallisation Methods 0.000 abstract description 4
- 230000008025 crystallization Effects 0.000 abstract description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract 2
- 238000000975 co-precipitation Methods 0.000 abstract 2
- 238000001914 filtration Methods 0.000 abstract 1
- 239000011780 sodium chloride Substances 0.000 abstract 1
- 239000011575 calcium Substances 0.000 description 22
- 239000004677 Nylon Substances 0.000 description 18
- 229920001778 nylon Polymers 0.000 description 18
- 239000011248 coating agent Substances 0.000 description 14
- 238000000576 coating method Methods 0.000 description 14
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Inorganic materials [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 13
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Inorganic materials [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 13
- 239000000843 powder Substances 0.000 description 12
- 229910052706 scandium Inorganic materials 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 7
- WLQXPAUZYVXSNE-UHFFFAOYSA-N [Ca].O[N+]([O-])=O Chemical compound [Ca].O[N+]([O-])=O WLQXPAUZYVXSNE-UHFFFAOYSA-N 0.000 description 6
- 229940043430 calcium compound Drugs 0.000 description 6
- 210000003298 dental enamel Anatomy 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 238000007873 sieving Methods 0.000 description 6
- 239000000037 vitreous enamel Substances 0.000 description 6
- XDFCIPNJCBUZJN-UHFFFAOYSA-N barium(2+) Chemical compound [Ba+2] XDFCIPNJCBUZJN-UHFFFAOYSA-N 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 229910052788 barium Inorganic materials 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J1/00—Details of electrodes, of magnetic control means, of screens, or of the mounting or spacing thereof, common to two or more basic types of discharge tubes or lamps
- H01J1/02—Main electrodes
- H01J1/13—Solid thermionic cathodes
- H01J1/14—Solid thermionic cathodes characterised by the material
- H01J1/142—Solid thermionic cathodes characterised by the material with alkaline-earth metal oxides, or such oxides used in conjunction with reducing agents, as an emissive material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J1/00—Details of electrodes, of magnetic control means, of screens, or of the mounting or spacing thereof, common to two or more basic types of discharge tubes or lamps
- H01J1/02—Main electrodes
- H01J1/13—Solid thermionic cathodes
- H01J1/14—Solid thermionic cathodes characterised by the material
- H01J1/144—Solid thermionic cathodes characterised by the material with other metal oxides as an emissive material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J9/00—Apparatus or processes specially adapted for the manufacture, installation, removal, maintenance of electric discharge tubes, discharge lamps, or parts thereof; Recovery of material from discharge tubes or lamps
- H01J9/02—Manufacture of electrodes or electrode systems
Abstract
The present invention relates to illuminating material field, a kind of electronic emission material of resistance to bombardment and preparation method thereof is disclosed.The electronic emission material of resistance to bombardment includes the material of following mass parts：52 56 parts of Ba (CO)2, 30 34 parts of Sr (CO)2, 10 15 parts of Ca (CO)2, 13 parts of rare earth oxides.Preparation method is to weigh Ba (NO by proportioning3)2Solution, Sr (NO3)2Solution, Ca (NO3)2Solution is simultaneously well mixed, and mixed nitrate saline solution is made, and (NH is instilled into the mixed nitrate saline solution4)2CO3Solution obtains co-precipitation crystallization, and co-precipitation crystallization drying, and the 56h of ball milling 40 are taken after filtering, CeO is eventually adding2And the well mixed electronic emission material that resistance to bombardment is just made.The electronic emission material of the resistance to bombardment of the present invention has that caking property is good, resistance to particle bombardment is good, low work function the characteristics of, being capable of effective prolonging lamp tube service life.
Description
Technical field
The present invention relates to illuminating material field, more particularly to a kind of electronic emission material of resistance to bombardment and preparation method thereof.
Background technology
Cathode fluorescent tube is on startup because the cathodic sputtering that the bombardment of strong cation is caused can be such that negative electrode causes greatly
Damage, so as to highly shortened the life-span of lamp.Ba (CO) in usual electronic powder2：Sr(CO)2：Ca(CO)2Mass ratio
About 53：40：7, in order to which the resistance to bombardment ability for increasing negative electrode can add 5% ZrO toward contact2。
The composition of triplex carbonate in novel electron emissive material, species, species, the ratio of the shape of crystallization and additive
Have a great impact etc. the anticathode performance of factor.
Wherein Ca (CO)2Effect be to strengthen the cementability of coating and filament to reduce electronic powder because Ions Bombardment is de-
Fall, but Ca (CO)2Decomposition temperature be 600 DEG C, and the CaO of generation after decomposing easily distils, thus during exhaust
There is loss.
ZrO2The resistance to bombardment ability of electronic powder can be improved, the loss of calcium activated is reduced, but can be caused and BaO2Reaction disappears
The too many active barium of consumption is so as to increase the work function on surface, and electron emission capability degenerates.
Therefore develop that a kind of caking property is good, resistance to particle bombardment is good, low work function electronic emission material is highly desirable to.
The content of the invention
In order to solve the above-mentioned technical problem, the invention provides a kind of electronic emission material of resistance to bombardment and its preparation side
Method.The electronic emission material of the resistance to bombardment of the present invention has that caking property is good, resistance to particle bombardment is good, low work function the characteristics of, can
Effectively extend the life-span of lamp.
The present invention concrete technical scheme be：A kind of electronic emission material of resistance to bombardment, includes the material of following mass parts：
52-56 parts of Ba (CO)2,
30-34 parts of Sr (CO)2,
10-15 parts of Ca (CO)2,
1-3 parts of rare earth oxides.
Preferably, the rare earth oxide is CeO2。
Cathode fluorescent tube is on startup because the cathodic sputtering that the bombardment of strong cation is caused can be such that negative electrode causes greatly
Damage, so as to highly shortened the life-span of lamp.Ba (CO) in usual electronic powder2：Sr(CO)2：Ca(CO)2Mass ratio
About 53：40：7, in order to which the resistance to bombardment ability for increasing negative electrode can add 5% ZrO toward contact2.Three in novel electron emissive material
The anticathode performance of factor such as the composition of first carbonate, species, species, the ratio of the shape of crystallization and additive has very big shadow
Ring.
Wherein Ca (CO)2Effect be to strengthen the cementability of coating and filament to reduce electronic powder because Ions Bombardment is de-
Fall, but Ca (CO)2Decomposition temperature be 600 DEG C, and the CaO of generation after decomposing easily distils, thus during exhaust
There is loss.Therefore after numerous studies, on the premise of other performances of emissive material are not substantially influenceed, the present invention is banged resistance to
Ca (CO) in the electronic emission material hit2Amount adjusted.
ZrO2The resistance to bombardment ability of electronic powder can be improved, the loss of calcium activated is reduced, but can be caused and BaO2Reaction disappears
The too many active barium of consumption is so as to increase the work function on surface, and electron emission capability degenerates.The electron emission of the resistance to bombardment of the present invention
Rare earth oxide is added with material, because rare earth oxide there are following features：Work function is low, between 2-3eV；Rare earth oxide
Relatively stablize and be difficult to volatilize, be amenable to 1500 DEG C of high temperature, the operating temperature of general negative electrode is between 950-1100 DEG C；Anti- poisoning energy
Power is strong, and resistance to Ions Bombardment.Therefore rare earth oxide can improve this property condition, therefore the present invention is in electronic emission material
Formula adjusted, make electronic emission material have caking property it is good, resistance to Ions Bombardment is good, low work function the advantages of.
Preferably, the electronic emission material of the resistance to bombardment by following mass parts material composition：
54 parts of Ba (CO)2,
32 parts of Sr (CO)2,
14 parts of Ca (CO)2,
2 parts of CeO2。
Preferably, the electronic emission material of the resistance to bombardment also includes 0.5-1.5 parts Sc and 0.5-1.5 parts
Sc2O3。
The present invention adds Sc and Sc in launching electronics material2O3,
The length in ordinary oxide electrode life-span under high current density is mainly determined by the semiconductor property of coated substance
Fixed.Because conductivity is high, work as high current（When particularly negative electrode is preheated）When, coating produce Joule heat can make BaO and
Ba seriously evaporates in coating surface, or even can occur the hardened phenomenon of coating melting, can cause the loss of emitting material.The present invention exists
Sc and Sc is added in launching electronics material2O3So that these phenomenons will not be produced when negative electrode is operated in high current.
Another aspect electric current flows through coating it also occur that electrolysis, the semiconductor property of coating causes in coating in appearance
Electric field E, and filament metal is pointed to, cause O in BaO crystal grain2-Ion and Ba2+Ion makees moving type transition in lattice defect,
Coating surface discharges O2, increase oxygen vacancy in lattice, Ba donor concentrations are improved, and Ba2+Ion is then migrated to filament direction,
Electronics is obtained on filament metal and becomes Ba atoms, the near interface of coating and filament is gathered in, part of Ba atom is towards coating
Interior diffusion, is conducive to spreading in transmitting, another part filament, on the crystal boundary full of filament, is unfavorable for transmitting.Therefore in high current
And under high vacuum condition, what the direction that BaO thermal decompositions in itself and electrolysis are advantageous for alms giver Ba was carried out.In the later stage in life-span,
The reduction that active element rises becomes secondary.So it is not that influence oxide-coated cathode is stable that active element is obstructed in intermediate layer
The main cause of work.
The present invention adds Sc and Sc in launching electronics material2O3, Sc and Sc in the cathode2O3The mechanism of action be：Coating
In Ba2+, O2-, Sc3+ ion has stronger interaction, makes Ba2+, O2-Ion departs from the energy threshold increase of lattice position,
So as to restrained effectively Ba2+, O2-Migration, diffusion with evaporation.Sc2O3Itself it is not effective emitter, but composite oxygen
The carrier function that compound rises in the coating, makes BaO at high temperature not hardened；The presence of Sc elements, improves the conduction of coating
Property, cathode temperature is evenly distributed, make the decay of negative electrode slow；So as to extend the life-span.
Preferably, the electronic emission material of the resistance to bombardment by following mass parts material composition：
54 parts of Ba (CO)2,
32 parts of Sr (CO)2,
14 parts of Ca (CO)2,
2 parts of CeO2,
1 part of Sc,
1 part of Sc2O3。
A kind of preparation method of the electronic emission material of resistance to bombardment, comprises the following steps：
Carbonic acid ammonia is added in 38-42 DEG C of pure water and stirred evenly, rear addition ammoniacal liquor to be dissolved simultaneously stirs 4-6min, makes solution
PH is 7-8, and mixed solution is made；Ba (NO are weighed respectively by proportioning3)2, Sr (NO3)2, Ca (NO3)2And be well mixed, it is made mixed
Close nitrate and the phase is dissolved in boiled pure water, be incubated to 80-84 DEG C, mixed solution drop obtained above is added dropwise and does not stop
Stirring, temperature control is at 75-80 DEG C, until complete reaction precipitation, is again heated to boiling, stops heating and standing 25-35min,
Cleaned after upper liquid is outwelled with 80-90 DEG C of pure water, standing 8-12min is washed every time, then upper liquid is outwelled into addition equivalent
Pure water clean again, 10 times repeatedly；Then successively by vacuum filtration, 130-140 DEG C of drying 20-28h adds CeO2, ball
Grind 40-56h；Finally cross after 300-350 mesh sub-sieves and the electronic emission material of resistance to bombardment is just made.
A kind of preparation method of the electronic emission material of resistance to bombardment, comprises the following steps：
Carbonic acid ammonia is added in 38-42 DEG C of pure water and stirred evenly, rear addition ammoniacal liquor to be dissolved simultaneously stirs 4-6min, makes solution
PH is 7-8, and mixed solution is made；Ba (NO are weighed respectively by proportioning3)2, Sr (NO3)2, Ca (NO3)2And be well mixed, it is made mixed
Close nitrate and the phase is dissolved in boiled pure water, be incubated to 80-84 DEG C, mixed solution drop obtained above is added dropwise and does not stop
Stirring, temperature control is at 75-80 DEG C, until complete reaction precipitation, is again heated to boiling, stops heating and standing 25-35min,
Cleaned after upper liquid is outwelled with 80-90 DEG C of pure water, standing 8-12min is washed every time, then upper liquid is outwelled into addition equivalent
Pure water clean again, 10 times repeatedly；Then successively by vacuum filtration, 130-140 DEG C of drying 20-28h adds CeO2、Sc
And Sc2O3Ball milling 40-56h；Finally cross after 300-350 mesh sub-sieves and the electronic emission material of resistance to bombardment is just made.
The reaction equation synthesized in above process is：Ca(NO3)2+Ba(NO3)2+Sr(NO3)2+(NH4)2CO3+NH3·H2O
→（Ba·Sr·Ca）CO3↓+NH4NO3
It is compared with the prior art, the beneficial effects of the invention are as follows：The electronic emission material of the resistance to bombardment of the present invention has viscous
Good, resistance to particle bombardment is good for knot property, low work function the characteristics of, be capable of the life-span of effective prolonging lamp tube.The fluorescent tube on-off times being made
40-50% can be increased.
Embodiment
With reference to embodiment, the invention will be further described.
Embodiment 1
A kind of electronic emission material of resistance to bombardment, includes the material of following mass parts：
54 parts of Ba (CO)2,
32 parts of Sr (CO)2,
14 parts of Ca (CO)2,
2 parts of CeO2。
A kind of preparation method of the electronic emission material of resistance to bombardment：
Carbonic acid ammonia is put into and heated in 40 DEG C of pure water, is stirred evenly with nylon rod, after after all dissolvings, is measured with graduated cylinder
Must the ammoniacal liquor of the amount of being be put into, and stir 5min, make its acid-base value between 7-8, be fitted into bottle, with the rubber of carrying pipe
Plug is covered.One of conduit is dropper.
Barium nitrate, strontium nitrate, nitric acid calcium compound are put into porcelain enamel barrel by proportioning, then boiled pure water is poured into,
Stirred with nylon rod, until mixture all dissolves.82 DEG C are heated to, the solution instilled in bottle does not stop stirring, temperature
Control is at 77.5 DEG C.Until complete reaction precipitation.Boiling is again heated to, stops standing 30min on heating cover, upper liquid is fallen
Fall, be transferred to be washed in Plastic Drum.Cleaned with 85 DEG C of pure water, standing 10min is washed every time, upper liquid is outwelled into addition equivalent
Pure water wash again, 10 times repeatedly.Vacuum filtration, untill draining；Powder is filled with enamel tray, filter paper is covered, 135 DEG C are dried 24 hours；
Add CeO2, ball milling 28h, with the sieving of 300-350 mesh nylon sub-sieve.Get product.
Embodiment 2
A kind of electronic emission material of resistance to bombardment, includes the material of following mass parts：
52 parts of Ba (CO)2,
34 parts of Sr (CO)2,
15 parts of Ca (CO)2,
1 part of CeO2。
A kind of preparation method of the electronic emission material of resistance to bombardment：
Carbonic acid ammonia is put into and heated in 38 DEG C of pure water, is stirred evenly with nylon rod, after after all dissolvings, is measured with graduated cylinder
Must the ammoniacal liquor of the amount of being be put into, and stir 4min, make its acid-base value between 7-8, be fitted into bottle, with the rubber of carrying pipe
Plug is covered.One of conduit is dropper.
Barium nitrate, strontium nitrate, nitric acid calcium compound are put into porcelain enamel barrel by proportioning, then boiled pure water is poured into,
Stirred with nylon rod, until mixture all dissolves.80 DEG C are heated to, the solution instilled in bottle does not stop stirring, temperature
Control is at 75 DEG C.Until complete reaction precipitation.Boiling is again heated to, stops standing 25min on heating cover, upper liquid is outwelled,
It is transferred to be washed in Plastic Drum.Cleaned with 80 DEG C of pure water, standing 8min is washed every time, upper liquid is outwelled and adds the pure of equivalent
Water purification is washed again, 10 times repeatedly.Vacuum filtration, untill draining；Powder is filled with enamel tray, filter paper is covered, 130 DEG C are dried 20 hours；Add
CeO2, ball milling 40h, with the sieving of 300-350 mesh nylon sub-sieve.Get product.
Embodiment 3
A kind of electronic emission material of resistance to bombardment, includes the material of following mass parts：
56 parts of Ba (CO)2,
30 parts of Sr (CO)2,
10 parts of Ca (CO)2,
3 parts of CeO2。
A kind of preparation method of the electronic emission material of resistance to bombardment：
Carbonic acid ammonia is put into and heated in 42 DEG C of pure water, is stirred evenly with nylon rod, after after all dissolvings, is measured with graduated cylinder
Must the ammoniacal liquor of the amount of being be put into, and stir 6min, make its acid-base value between 7-8, be fitted into bottle, with the rubber of carrying pipe
Plug is covered.One of conduit is dropper.
Barium nitrate, strontium nitrate, nitric acid calcium compound are put into porcelain enamel barrel by proportioning, then boiled pure water is poured into,
Stirred with nylon rod, until mixture all dissolves.84 DEG C are heated to, the solution instilled in bottle does not stop stirring, temperature
Control is at 80 DEG C.Until complete reaction precipitation.Boiling is again heated to, stops standing 25min on heating cover, upper liquid is outwelled,
It is transferred to be washed in Plastic Drum.Cleaned with 90 DEG C of pure water, standing 12min is washed every time, upper liquid is outwelled and adds equivalent
Pure water is washed again, 10 times repeatedly.Vacuum filtration, untill draining；Powder is filled with enamel tray, filter paper is covered, 140 DEG C are dried 28 hours；Plus
Enter CeO2, ball milling 56h, with the sieving of 300-350 mesh nylon sub-sieve.Get product.
Embodiment 4
A kind of electronic emission material of resistance to bombardment, includes the material of following mass parts：
54 parts of Ba (CO)2,
32 parts of Sr (CO)2,
12.5 parts of Ca (CO)2,
2 parts of CeO2,
1 part of Sc,
1 part of Sc2O3。
A kind of preparation method of the electronic emission material of resistance to bombardment：
Carbonic acid ammonia is put into and heated in 40 DEG C of pure water, is stirred evenly with nylon rod, after after all dissolvings, is measured with graduated cylinder
Must the ammoniacal liquor of the amount of being be put into, and stir 5min, make its acid-base value between 7-8, be fitted into bottle, with the rubber of carrying pipe
Plug is covered.One of conduit is dropper.
Barium nitrate, strontium nitrate, nitric acid calcium compound are put into porcelain enamel barrel by proportioning, then boiled pure water is poured into,
Stirred with nylon rod, until mixture all dissolves.82 DEG C are heated to, the solution instilled in bottle does not stop stirring, temperature
Control is at 77.5 DEG C.Until complete reaction precipitation.Boiling is again heated to, stops standing 30min on heating cover, upper liquid is fallen
Fall, be transferred to be washed in Plastic Drum.Cleaned with 85 DEG C of pure water, standing 10min is washed every time, upper liquid is outwelled into addition equivalent
Pure water wash again, 10 times repeatedly.Vacuum filtration, untill draining；Powder is filled with enamel tray, filter paper is covered, 135 DEG C are dried 24 hours；
Add CeO2, Sc and Sc2O3, ball milling 28h, with the sieving of 300-350 mesh nylon sub-sieve.Get product.
Embodiment 5
A kind of electronic emission material of resistance to bombardment, includes the material of following mass parts：
52 parts of Ba (CO)2,
34 parts of Sr (CO)2,
15 parts of Ca (CO)2,
1 part of CeO2,
0.5 part of Sc,
0.5 part of Sc2O3。
A kind of preparation method of the electronic emission material of resistance to bombardment：
Carbonic acid ammonia is put into and heated in 38 DEG C of pure water, is stirred evenly with nylon rod, after after all dissolvings, is measured with graduated cylinder
Must the ammoniacal liquor of the amount of being be put into, and stir 4min, make its acid-base value between 7-8, be fitted into bottle, with the rubber of carrying pipe
Plug is covered.One of conduit is dropper.
Barium nitrate, strontium nitrate, nitric acid calcium compound are put into porcelain enamel barrel by proportioning, then boiled pure water is poured into,
Stirred with nylon rod, until mixture all dissolves.80 DEG C are heated to, the solution instilled in bottle does not stop stirring, temperature
Control is at 75 DEG C.Until complete reaction precipitation.Boiling is again heated to, stops standing 25min on heating cover, upper liquid is outwelled,
It is transferred to be washed in Plastic Drum.Cleaned with 80 DEG C of pure water, standing 8min is washed every time, upper liquid is outwelled and adds the pure of equivalent
Water purification is washed again, 10 times repeatedly.Vacuum filtration, untill draining；Powder is filled with enamel tray, filter paper is covered, 130 DEG C are dried 20 hours；Add
CeO2, Sc and Sc2O3, ball milling 40h, with the sieving of 300-350 mesh nylon sub-sieve.Get product.
Embodiment 6
A kind of electronic emission material of resistance to bombardment, includes the material of following mass parts：
By the material composition of following mass parts：
56 parts of Ba (CO)2,
30 parts of Sr (CO)2,
10 parts of Ca (CO)2,
3 parts of CeO2,
1.5 parts of Sc,
1.5 parts of Sc2O3。
A kind of preparation method of the electronic emission material of resistance to bombardment：
Carbonic acid ammonia is put into and heated in 42 DEG C of pure water, is stirred evenly with nylon rod, after after all dissolvings, is measured with graduated cylinder
Must the ammoniacal liquor of the amount of being be put into, and stir 6min, make its acid-base value between 7-8, be fitted into bottle, with the rubber of carrying pipe
Plug is covered.One of conduit is dropper.
Barium nitrate, strontium nitrate, nitric acid calcium compound are put into porcelain enamel barrel by proportioning, then boiled pure water is poured into,
Stirred with nylon rod, until mixture all dissolves.84 DEG C are heated to, the solution instilled in bottle does not stop stirring, temperature
Control is at 80 DEG C.Until complete reaction precipitation.Boiling is again heated to, stops standing 25min on heating cover, upper liquid is outwelled,
It is transferred to be washed in Plastic Drum.Cleaned with 90 DEG C of pure water, standing 12min is washed every time, upper liquid is outwelled and adds equivalent
Pure water is washed again, 10 times repeatedly.Vacuum filtration, untill draining；Powder is filled with enamel tray, filter paper is covered, 140 DEG C are dried 28 hours；Plus
Enter CeO2, Sc and Sc2O3, ball milling 56h, with the sieving of 300-350 mesh nylon sub-sieve.Get product.
Comparative example
53 parts of Ba (CO)2,
40 parts of Sr (CO)2,
7 parts of Ca (CO)2,
5 parts of ZrO2
Embodiment 1-6 electronic emission material has that caking property is good, resistance to particle bombardment is good, low work function the characteristics of, can
The life-span of effective prolonging lamp tube.The fluorescent tube being made is compared with the fluorescent tube that comparative example is made, and on-off times can increase 40-50%.
Raw materials used in the present invention, equipment, is the conventional raw material, equipment of this area unless otherwise noted；In the present invention
Method therefor, is the conventional method of this area unless otherwise noted.
It is described above, only it is presently preferred embodiments of the present invention, not the present invention is imposed any restrictions, it is every according to the present invention
Any simple modification, change and equivalent transformation that technical spirit is made to above example, still fall within the technology of the present invention side
The protection domain of case.
Claims (2)
1. a kind of electronic emission material of resistance to bombardment, it is characterised in that include the material of following mass parts：
54 parts of BaCO3,
32 parts of SrCO3,
14 parts of CaCO3,
2 parts of CeO2,
1 part of Sc,
1 part of Sc2O3。
2. a kind of a kind of preparation method of the electronic emission material of resistance to bombardment as claimed in claim 1, it is characterised in that including
Following steps：
Carbonic acid ammonia is added in 38-42 DEG C of pure water and stirred evenly, it is to be dissolved after add ammoniacal liquor and simultaneously stir 4-6min, make the pH value of solution be
7-8, is made mixed solution；Ba (NO are weighed respectively by proportioning3)2, Sr (NO3)2, Ca (NO3)2And be well mixed, mixing nitre is made
Phase is simultaneously dissolved in boiled pure water by hydrochlorate, is incubated to 80-84 DEG C, and mixed solution drop obtained above is added dropwise and does not stop to stir
Mix, temperature control is at 75-80 DEG C, until complete reaction precipitation, is again heated to boiling, stops heating and stand 25-35min, will
Upper liquid is cleaned after outwelling with 80-90 DEG C of pure water, standing 8-12min is washed every time, then upper liquid is outwelled into addition equivalent
Pure water is cleaned again, 10 times repeatedly；Then successively by vacuum filtration, 130-140 DEG C of drying 20-28h adds CeO2, Sc and
Sc2O3Ball milling 40-56h；Finally cross after 300-350 mesh sub-sieves and the electronic emission material of resistance to bombardment is just made.
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Cited By (1)
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| CN110690085A (en) * | 2019-10-24 | 2020-01-14 | 成都国光电气股份有限公司 | Method for preparing quaternary cathode emission material |
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