CN108751243A - Preparation method of aluminate electron emission material for impregnated cathode - Google Patents
Preparation method of aluminate electron emission material for impregnated cathode Download PDFInfo
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- CN108751243A CN108751243A CN201810332467.4A CN201810332467A CN108751243A CN 108751243 A CN108751243 A CN 108751243A CN 201810332467 A CN201810332467 A CN 201810332467A CN 108751243 A CN108751243 A CN 108751243A
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- 150000004645 aluminates Chemical class 0.000 title claims abstract description 44
- 239000000463 material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims abstract description 114
- 239000000243 solution Substances 0.000 claims abstract description 91
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims abstract description 67
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims abstract description 28
- 238000001354 calcination Methods 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 239000012266 salt solution Substances 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 13
- 238000005303 weighing Methods 0.000 claims abstract description 11
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000975 co-precipitation Methods 0.000 claims abstract description 10
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000292 calcium oxide Substances 0.000 claims abstract description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 239000003153 chemical reaction reagent Substances 0.000 claims description 13
- 230000001376 precipitating effect Effects 0.000 claims description 13
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 12
- 239000001099 ammonium carbonate Substances 0.000 claims description 12
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 12
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 10
- 229910052791 calcium Inorganic materials 0.000 claims description 10
- 239000011575 calcium Substances 0.000 claims description 10
- 239000011268 mixed slurry Substances 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 239000000908 ammonium hydroxide Substances 0.000 claims description 8
- 230000003993 interaction Effects 0.000 claims description 6
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 5
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 5
- 239000004571 lime Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000004876 x-ray fluorescence Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- -1 nitric acid aluminum Chemical compound 0.000 claims description 2
- 238000000643 oven drying Methods 0.000 claims 1
- 238000005979 thermal decomposition reaction Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract 3
- 238000001035 drying Methods 0.000 abstract 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000005118 spray pyrolysis Methods 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 238000010586 diagram Methods 0.000 description 8
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 239000013049 sediment Substances 0.000 description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 4
- 239000010937 tungsten Substances 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 238000002242 deionisation method Methods 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- WMTSAHAFZXEJBV-UHFFFAOYSA-N [Ba].[W] Chemical compound [Ba].[W] WMTSAHAFZXEJBV-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical class [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229910052571 earthenware Inorganic materials 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229940126680 traditional chinese medicines Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/16—Preparation of alkaline-earth metal aluminates or magnesium aluminates; Aluminium oxide or hydroxide therefrom
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention provides a preparation method of an aluminate electron emission material for an impregnated cathode, which comprises the following specific steps: (1) accurately weighing barium nitrate, calcium nitrate and aluminum nitrate solution, drying and calcining, and accurately weighing the mass of the obtained calcined barium nitrate, calcium oxide and aluminum oxide; (2) accurately measuring the purity of the calcined barium nitrate, calcium oxide and aluminum oxide; (3) calculating the mass of pure barium nitrate, calcium oxide and aluminum oxide obtained by drying and calcining 100 g of barium nitrate solution, calcium nitrate solution and aluminum nitrate solution; (4) calculating the weight of barium nitrate, calcium nitrate and aluminum nitrate solution according to the chemical composition and weight of aluminate to be prepared; (5) weighing barium nitrate, calcium nitrate and aluminum nitrate solution according to the calculation result, and mixing to obtain mixed salt solution for coprecipitation synthesis of the aluminate electron emission material; (6) the aluminate electron emission material is prepared by adopting a coprecipitation and spray pyrolysis combined process. The invention has reasonable process design, is simple and easy to operate; the chemical composition of the prepared aluminate can be accurately controlled, and the crystallinity is complete.
Description
Technical field
The invention belongs to microwave electron tube manufacturing fields, and in particular to a kind of dipped cathode aluminate electronics hair
Penetrate material preparation method.
Background technology
Cathode is microwave electrovacuum electronic device " heart ", the property such as power output and service life to HIGH-POWERED MICROWAVES device
It can play a crucial role.Immersion-type barium-tungsten dispense cathode is by porous tungsten basal body and to be immersed in aluminate electron emission therein
Material is formed, and has the characteristics such as emission is big, anti-toxicity energy is excellent, in, powerful microwave electrovacuum electricity
It is most widely used in sub- device.The quality of immersion-type barium-tungsten dispense cathode performance depends primarily on aluminate electronic emission material chemistry
Composition and the uniformity of each element composition distribution.Researcher has found that using chemical coprecipitation technique synthesizing aluminate can be improved
The uniformity that studies point, the granularity for reducing aluminate；But the accuracy for how improving aluminate chemical composition with it is consistent
But without effective measures in property.Application No. is 201110284836.5 Chinese patents to disclose a kind of multi-injection cathode activity
Substances preparation method is prepared using nine water aluminum nitrates, four water-calcium nitrate, barium nitrate and ammonium carbonate as raw material using coprecipitation method
Aluminate.The patent and most literature report, coprecipitation reaction mixing will be configured to after the directly weighing of commercially available nitrate
Salting liquid；And building-up process needs the operations such as to be filtered coprecipitated product, wash.It is micro- due to containing in commercially available nitrate
Measure impurity, the absorption water and crystallization water, by directly weigh it is hardly possible obtain that each element component proportion accurately controls be total to
Precipitation reaction mixing salt solution, this will cause the aluminate chemical composition synthesized can not be designed to point be consistent；
Moreover, when raw material batch or producer replace, the consistency of synthesizing aluminate composition and its performance is also unable to get guarantee；This
Outside, coprecipitated product will produce during being filtered, washed and be partly dissolved and the ingredient of aluminate be caused to change.
Invention content
The purpose of the present invention is overcome the deficiencies of the prior art and provide a kind of dipped cathode aluminate electron emission material
Preparation method for material.
The present invention solve technical problem the technical solution adopted is that：A kind of dipped cathode aluminate electronic emission material
Preparation method, be as follows：
(1) barium nitrate and deionized water are configured to certain density barium nitrate solution, weight is poured into after weighing constant weight
Amount is Wg1Gram, be fired to the crucible of constant weight, weigh exact mass W of the solution together with cruciblebg1Gram, crucible is first placed into baking
It is dried in case, then is placed in electric furnace and is fired to constant weight at 200~500 DEG C, weigh accurate weight W of the calcined product together with cruciblebg2
Gram, the weight for obtaining calcining barium nitrate is (Wbg2-Wg1) gram；Calcium nitrate and deionized water are configured to certain density calcium nitrate
Solution pours into weight as W after weighing constant weightg2Gram, be fired to the crucible of constant weight, weigh accurate matter of the solution together with crucible
Measure Wcg1Gram, crucible is first placed into baking oven and is dried, then is placed in electric furnace and is fired to constant weight at 800~1250 DEG C, weighs calcining
Accurate weight W of the product together with cruciblecg2Gram, the weight for obtaining calcined oxide calcium is (Wcg2-Wg2) gram；By aluminum nitrate and deionization
Water is configured to certain density aluminum nitrate solution, and weight is poured into as W after weighing constant weightg3Gram, be fired to the crucible of constant weight,
Weigh exact mass W of the solution together with crucibleag1Gram, crucible is first placed into baking oven and is dried, then be placed in electric furnace 800~
1250 DEG C are fired to constant weight, weigh accurate weight W of the calcined product together with crucibleag2Gram, the weight for obtaining calcined alumina is
(Wag2-Wg3) gram；
(2) the calcining barium nitrate prepared in the accurate determination step of X-ray fluorescence spectrometer (1), calcined oxide are used
The purity C of barium nitrate in calcium and calcined aluminab0, calcium oxide purity Cc0With the purity C of aluminium oxidea0；
(3) the exact mass M of pure barium nitrate can be obtained by calculating after every 100 grams of barium nitrate solution is calcinedb0, Mb0=100 ×
(Wbg2-Wg1)/(Wbg1-Wg1)×Cb0；The exact mass of carbonate-free lime can be obtained by calculating after every 100 grams of calcium nitrate solutions are calcined
Mc0, Mc0=100 × (Wcg2-Wg2)/(Wcg1-Wg2)×Cc0；Pure zirconia can be obtained after calculating every 100 grams of aluminum nitrate solutions calcining
The exact mass M of aluminiuma0, Ma0=100 × (Wag2-Wg3)/(Wag1-Wg3)×Ca0；
(4) it is xBaOyCaOzAl to calculate and prepare chemical composition2O3L grams of aluminate needed for barium nitrate solution weight
Wb1=(L × 26134 × x)/(153.33x+56.08y+101.96z)/Mb0, required calcium nitrate solution weight Wc1=(5608 × y
×L)/(153.33x+56.08y+101.96z)/Mc0, required aluminum nitrate solution weight Wa1=(10196 × z × L)/
(153.33x+56.08y+101.96z)/Ma0；
(5) precise barium nitrate solution Wb1Gram, calcium nitrate solution Wc1Gram and aluminum nitrate solution Wa1Gram, it is mixed equal
Aluminate electronic emission material coprecipitation mixing salt solution is prepared after even；
(6) mixing salt solution for taking a certain amount of step (5) to prepare, is added dropwise precipitating reagent thereto while stirring, until solution
PH value stops being added dropwise when reaching 8.2~8.8, obtains with precipitated product mixed slurry as main component；Mixed slurry is sprayed into
In spray-wall interaction stove, collects powder and obtain dipped cathode aluminate electronic emission material.
Crucible material is aluminium oxide in preferred steps 1, and content is more than 99%, is calcined in 1300~1400 DEG C of electric furnace
To constant weight.
The pureness specifications of barium nitrate, calcium nitrate and nitric acid aluminum feedstock are that chemistry is pure in preferred steps 1；Prepared barium nitrate is molten
The mass concentration of liquid is 4~12%, and the mass concentration of calcium nitrate solution is 20~45%, and the mass concentration of aluminum nitrate solution is 15
~25%.
It is 1.7~2.2 by weight that precipitating reagent in preferred steps 6, which is by ammonium carbonate and ammonium hydroxide,:1 is dissolved in deionized water
The mixed solution prepared afterwards, the wherein mass concentration of ammonium hydroxide are 25~28%；The mass concentration of ammonium carbonate is 10 in mixed solution
~25%, it is pure that the pureness specifications of ammonium carbonate and ammonium hydroxide are at least chemistry.
Precipitated product is BaCO in preferred steps 63、BaCa(CO3)2With amorphous AOOH.
The temperature of spray-wall interaction stove is 1250~1500 DEG C in preferred steps 6.
Advantageous effect：
(1) dipped cathode of the present invention aluminate electronic emission material preparation method, technological design are reasonable, simple
It is single easily operated.
(2) dipped cathode of the present invention aluminate electronic emission material preparation method, synthesized precipitated product
Granularity is small, Elemental redistribution is uniform, prepares the chemical composition of aluminate electronic emission material and can accurately control, and crystallinity is intact,
Emission is big, and consistency of performance, repeatability and stability are good.
Description of the drawings
Fig. 1 is the XRD diagram of precipitated product prepared by embodiment 1；
Fig. 2 is the XRD diagram of aluminate electronic emission material prepared by embodiment 1；
Fig. 3 is the XRD diagram of aluminate electronic emission material prepared by embodiment 2；
Fig. 4 is the XRD diagram of aluminate electronic emission material prepared by embodiment 3.
Specific implementation mode
It is the specific implementation case of the present invention below, notices that these cases are merely to illustrate the present invention rather than limitation originally
The range of invention.
Embodiment 1：
It is 4% that the pure barium nitrate of chemistry for being purchased from Xilong Chemical Co., Ltd is configured to mass concentration with deionized water
Barium nitrate solution, weigh pour into after constant weight constant weight is fired at 1300 DEG C, the crucible (aluminium oxide that weight is 255.15 grams
Content is 99.3%), to weigh solution together with 411.15 grams of the exact mass of crucible, crucible is first placed into 100 DEG C of baking ovens and is dried
24 hours, then be placed in electric furnace and be fired to constant weight at 200 DEG C, accurate weight 261.39 gram of the calcined product together with crucible is weighed,
The weight for obtaining calcining barium nitrate is 6.24 grams.The pure calcium nitrate of chemistry and deionization of Xilong Chemical Co., Ltd will be purchased from
Water is configured to the calcium nitrate solution that mass concentration is 20%, weighs to pour into after constant weight and is fired to constant weight, weight at 1300 DEG C
For 263.02 grams of crucibles (alumina content 99.3%), exact mass 419.76 gram of the solution together with crucible is weighed, by earthenware
Crucible, which is first placed into 150 DEG C of baking ovens, to be dried 12 hours, then is placed in electric furnace and is fired to constant weight at 800 DEG C, weigh calcined product together with
273.73 grams of the accurate weight of crucible, the weight for obtaining calcined oxide calcium are 10.71 grams.The western limited public affairs of Gansu Province chemical industry share will be purchased from
The pure aluminum nitrate of chemistry and the deionized water of department are configured to the aluminum nitrate solution that mass concentration is 15%, are poured into after weighing constant weight
It is fired to constant weight at 1300 DEG C, the crucible (alumina content 99.3%) that weight is 263.57 grams, weighs solution together with crucible
419.82 grams of exact mass, crucible is first placed into 120 DEG C of baking ovens and is dried 18 hours, then be placed in electric furnace at 800 DEG C calcine
To constant weight, accurate weight 269.18 gram of the calcined product together with crucible is weighed, the weight for obtaining calcined alumina is 5.61 grams.
Using X-ray fluorescence spectrometer (ARL ADVANT'XP) accurately measure calcining barium nitrate, calcined oxide calcium and
The purity of barium nitrate is 99.32% in calcined alumina, the purity of calcium oxide is 99.45% and the purity of aluminium oxide is
99.38%.
The exact mass of pure barium nitrate can be obtained by calculating after every 100 grams of barium nitrate solution is calcined be 3.9728 grams；It calculates
The exact mass that carbonate-free lime can be obtained after every 100 grams of calcium nitrate solutions calcining is 6.7954 grams；Calculate every 100 grams of aluminum nitrates
The exact mass that pure alumina can be obtained after solution calcining is 3.5681 grams.
It is 6BaOCaO2Al to calculate and prepare chemical composition2O3800 grams of aluminate needed for barium nitrate solution weight be
26759.36 grams, 559.51 grams of required calcium nitrate solution weight, 3874.66 grams of required aluminum nitrate solution weight.
3874.66 grams of 26759.36 grams of precise barium nitrate solution, 559.51 grams of calcium nitrate solution and aluminum nitrate solution,
Aluminate electronic emission material coprecipitation mixing salt solution is prepared after being mixed evenly.
It is 1.7 by weight with the pure ammonium carbonate of chemistry with ammonium hydroxide (mass concentration 25%) for raw material:1 be dissolved in from
It is prepared into precipitating reagent after sub- water, the mass concentration of ammonium carbonate is 10% in precipitating reagent.800 grams of mixing salt solutions are taken to pour into beaker,
Precipitating reagent is added dropwise into prepared mixing salt solution while stirring, until solution ph stops being added dropwise when reaching 8.2, is sunk
The XRD diagram of the mixed slurry of starch, sediment is shown in Fig. 1, and the object through sediment known to analysis is mutually BaCO3、BaCa(CO3)2With nothing
Shape AOOH；Mixed slurry is sprayed into 1250 DEG C of spray-wall interaction stove, collects powder and obtain dipped cathode aluminate
Electronic emission material, XRD diagram are shown in Fig. 2.Prepared aluminate is impregnated into porous tungsten basal body, diode is assembled to after cathode is made
In, reach 33.54A/cm in the emission that 1050 DEG C measure2。
Embodiment 2
The pure barium nitrate of chemistry for being purchased from Sinopharm Chemical Reagent Co., Ltd. is configured to mass concentration with deionized water
For 12% barium nitrate solution, weigh pour into after constant weight constant weight is fired at 1400 DEG C, the crucible that weight is 269.39 grams
(alumina content 99.5%) weighs solution together with 421.45 grams of the exact mass of crucible, crucible is first placed into 150 DEG C of bakings
It is dried 12 hours in case, then is placed in electric furnace and is fired to constant weight at 500 DEG C, weigh accurate weight of the calcined product together with crucible
287.64 grams, the weight for obtaining calcining barium nitrate is 18.25 grams.The chemistry for being purchased from Sinopharm Chemical Reagent Co., Ltd. is pure
Calcium nitrate and deionized water are configured to the calcium nitrate solution that mass concentration is 45%, weigh to pour into after constant weight and be forged at 1400 DEG C
It burns to constant weight, the crucible (alumina content 99.5%) that weight is 272.15 grams, weighs exact mass of the solution together with crucible
432.50 grams, crucible is first placed into 120 DEG C of baking ovens and is dried 18 hours, then is placed in electric furnace and is fired to constant weight at 1250 DEG C, claimed
Accurate weight 296.81 gram of the calcined product together with crucible is measured, the weight for obtaining calcined oxide calcium is 24.66 grams.Traditional Chinese medicines will be purchased from
The pure aluminum nitrate of chemistry and the deionized water of chemical reagent Co., Ltd of group are configured to the aluminum nitrate solution that mass concentration is 25%,
Weigh pour into after constant weight constant weight is fired at 1400 DEG C, (alumina content is for crucible that weight is 270.57 grams
99.5%) solution, is weighed together with 433.79 grams of the exact mass of crucible, and crucible is first placed into 100 DEG C of baking ovens and is dried 24 hours,
It is placed in again in electric furnace and is fired to constant weight at 1250 DEG C, weigh calcined product together with 280.34 grams of the accurate weight of crucible, forged
The weight for burning aluminium oxide is 9.77 grams.
Using X-ray fluorescence spectrometer (ARL ADVANT'XP) accurately measure calcining barium nitrate, calcined oxide calcium and
The purity of barium nitrate is 99.49% in calcined alumina, the purity of calcium oxide is 99.54% and the purity of aluminium oxide is
99.21%.
The exact mass of pure barium nitrate can be obtained by calculating after every 100 grams of barium nitrate solution is calcined be 11.9406 grams；It calculates
The exact mass that carbonate-free lime can be obtained after every 100 grams of calcium nitrate solutions calcining is 15.3081 grams；Calculate every 100 grams of nitric acid
The exact mass that pure alumina can be obtained after aluminum solutions calcining is 5.9385 grams.
It is 4BaOCaOAl to calculate and prepare chemical composition2O3800 grams of aluminate needed for barium nitrate solution weight be
9079.70 grams, 379.94 grams of required calcium nitrate solution weight, 1780.68 grams of required aluminum nitrate solution weight.
1780.68 grams of 9079.70 grams of precise barium nitrate solution, 379.94 grams of calcium nitrate solution and aluminum nitrate solution,
Aluminate electronic emission material coprecipitation mixing salt solution is prepared after being mixed evenly.
It is 2.2 by weight with the pure ammonium carbonate of chemistry with ammonium hydroxide (mass concentration 28%) for raw material:1 be dissolved in from
It is prepared into precipitating reagent after sub- water, the mass concentration of ammonium carbonate is 25% in precipitating reagent.500 grams of mixing salt solutions are taken to pour into beaker,
Precipitating reagent is added dropwise into prepared mixing salt solution while stirring, until solution ph stops being added dropwise when reaching 8.8, is sunk
The mixed slurry of starch, the object phase composition that sediment is dried with XRD determining is BaCO3、BaCa(CO3)2With amorphous AOOH；It will
Mixed slurry sprays into 1500 DEG C of spray-wall interaction stove, collects powder and obtains dipped cathode aluminate electron emission material
Material, XRD diagram are shown in Fig. 3.Prepared aluminate is impregnated into porous tungsten basal body, is assembled in diode after cathode is made, 1050
DEG C emission measured reaches 37.23A/cm2。
Embodiment 3：
The pure barium nitrate of chemistry for being purchased from Shanghai Aladdin biochemical technology limited liability company is configured to matter with deionized water
The barium nitrate solution for measuring a concentration of 8%, weigh pour into after constant weight constant weight is fired at 1400 DEG C, weight is 258.35 grams
Crucible (alumina content 99.7%) weighs solution together with 410.28 grams of the exact mass of crucible, crucible is first placed into 120
It is dried 18 hours in DEG C baking oven, then is placed in electric furnace and is fired to constant weight at 400 DEG C, weigh accurate weight of the calcined product together with crucible
270.50 grams, the weight for obtaining calcining barium nitrate is 12.15 grams.Shanghai Aladdin biochemical technology limited liability company will be purchased from
The pure calcium nitrate of chemistry is configured to the calcium nitrate solution that mass concentration is 30% with deionized water, is poured into after weighing constant weight
1400 DEG C are fired to constant weight, weight as 263.97 grams of crucible (alumina content 99.7%), weigh solution together with crucible
Crucible is first placed into 100 DEG C of baking ovens and dries 24 hours, then is placed in electric furnace and is fired at 1000 DEG C by 424.27 grams of exact mass
Constant weight weighs accurate weight 280.40 gram of the calcined product together with crucible, and the weight for obtaining calcined oxide calcium is 16.44 grams.It will
The pure aluminum nitrate of chemistry for being purchased from Shanghai Aladdin biochemical technology limited liability company is configured to mass concentration with deionized water and is
20% aluminum nitrate solution, weigh pour into after constant weight constant weight is fired at 1400 DEG C, the crucible (oxygen that weight is 258.39 grams
It is 99.7%), to weigh solution together with 424.53 grams of the exact mass of crucible, crucible is first placed into 150 DEG C of baking ovens to change aluminium content
It is middle to dry 12 hours, then be placed in electric furnace and be fired to constant weight at 1000 DEG C, weigh accurate weight of the calcined product together with crucible
266.34 grams, the weight for obtaining calcined alumina is 7.95 grams.
Using X-ray fluorescence spectrometer (ARL ADVANT'XP) accurately measure calcining barium nitrate, calcined oxide calcium and
The purity of barium nitrate is 99.28% in calcined alumina, the purity of calcium oxide is 99.31% and the purity of aluminium oxide is
99.47%.
The exact mass of pure barium nitrate can be obtained by calculating after every 100 grams of barium nitrate solution is calcined be 7.9395 grams；It calculates
The exact mass that carbonate-free lime can be obtained after every 100 grams of calcium nitrate solutions calcining is 10.1788 grams；Calculate every 100 grams of nitric acid
The exact mass that pure alumina can be obtained after aluminum solutions calcining is 4.7598 grams.
It is 3BaOCaOAl to calculate and prepare chemical composition2O31000 grams of aluminate needed for barium nitrate solution weight be
15978.02 grams, 891.46 grams of required calcium nitrate solution weight, 3466.05 grams of required aluminum nitrate solution weight.
3466.05 grams of 15978.02 grams of precise barium nitrate solution, 891.46 grams of calcium nitrate solution and aluminum nitrate solution,
Aluminate electronic emission material coprecipitation mixing salt solution is prepared after being mixed evenly.
It is 2 by weight with the pure ammonium carbonate of chemistry with ammonium hydroxide (mass concentration 26%) for raw material:1 is dissolved in deionization
It is prepared into precipitating reagent after water, the mass concentration of ammonium carbonate is 20% in precipitating reagent.600 grams of mixing salt solutions are taken to pour into beaker, side
Precipitating reagent is added dropwise into prepared mixing salt solution in stirring side, until solution ph stops being added dropwise when reaching 8.5, is precipitated
The mixed slurry of object, the object phase composition that sediment is dried with XRD determining is BaCO3、BaCa(CO3)2With amorphous AOOH；It will mix
It closes in the spray-wall interaction stove that slurry sprays into 1350 DEG C, collects powder and obtain dipped cathode aluminate electronic emission material,
Its XRD diagram is shown in Fig. 4.Prepared aluminate is impregnated into porous tungsten basal body, is assembled in diode after cathode is made, is surveyed at 1050 DEG C
The emission obtained reaches 30.15A/cm2。
Claims (6)
1. a kind of dipped cathode preparation method of aluminate electronic emission material, is as follows：
(1) barium nitrate and deionized water are configured to certain density barium nitrate solution, weigh and pours into weight after constant weight and be
Wg1Gram, be fired to the crucible of constant weight, weigh exact mass W of the solution together with cruciblebg1Gram, crucible is first placed into baking oven
Drying, then be placed in electric furnace and be fired to constant weight at 200~500 DEG C, weigh accurate weight W of the calcined product together with cruciblebg2Gram,
The weight for obtaining calcining barium nitrate is (Wbg2-Wg1) gram；It is molten that calcium nitrate with deionized water is configured to certain density calcium nitrate
Liquid pours into weight as W after weighing constant weightg2Gram, be fired to the crucible of constant weight, weigh exact mass of the solution together with crucible
Wcg1Gram, crucible is first placed into baking oven and is dried, then is placed in electric furnace and is fired to constant weight at 800~1250 DEG C, weighs calcining production
Accurate weight W of the object together with cruciblecg2Gram, the weight for obtaining calcined oxide calcium is (Wcg2-Wg2) gram；By aluminum nitrate and deionized water
It is configured to certain density aluminum nitrate solution, weight is poured into as W after weighing constant weightg3Gram, be fired to the crucible of constant weight, claim
Measure exact mass W of the solution together with crucibleag1Gram, crucible is first placed into baking oven and is dried, then be placed in electric furnace 800~
1250 DEG C are fired to constant weight, weigh accurate weight W of the calcined product together with crucibleag2Gram, the weight for obtaining calcined alumina is
(Wag2-Wg3) gram；
(2) use the accurate determination step of X-ray fluorescence spectrometer (1) in prepare calcining barium nitrate, calcined oxide calcium and
The purity C of barium nitrate in calcined aluminab0, calcium oxide purity Cc0With the purity C of aluminium oxidea0；
(3) the exact mass M of pure barium nitrate can be obtained by calculating after every 100 grams of barium nitrate solution is calcinedb0, Mb0=100 × (Wbg2-
Wg1)/(Wbg1-Wg1)×Cb0；The exact mass M of carbonate-free lime can be obtained by calculating after every 100 grams of calcium nitrate solutions are calcinedc0, Mc0
=100 × (Wcg2-Wg2)/(Wcg1-Wg2)×Cc0；The standard of pure alumina can be obtained by calculating after every 100 grams of aluminum nitrate solutions are calcined
True mass Ma0, Ma0=100 × (Wag2-Wg3)/(Wag1-Wg3)×Ca0；
(4) it is xBaOyCaOzAl to calculate and prepare chemical composition2O3L grams of aluminate needed for barium nitrate solution weight Wb1=(L
×26134×x)/(153.33x+56.08y+101.96z)/Mb0, required calcium nitrate solution weight Wc1=(5608 × y × L)/
(153.33x+56.08y+101.96z)/Mc0, required aluminum nitrate solution weight Wa1=(10196 × z × L)/(153.33x+
56.08y+101.96z)/Ma0；
(5) precise barium nitrate solution Wb1Gram, calcium nitrate solution Wc1Gram and aluminum nitrate solution Wa1Gram, after being mixed evenly
Aluminate electronic emission material coprecipitation mixing salt solution is prepared；
(6) mixing salt solution for taking a certain amount of step (5) to prepare, is added dropwise precipitating reagent thereto while stirring, until solution ph
Stop being added dropwise when reaching 8.2~8.8, obtain with precipitated product mixed slurry as main component；Mixed slurry is sprayed into and is sprayed
In thermal decomposition furnace, collects powder and obtain dipped cathode aluminate electronic emission material.
2. preparation method according to claim 1, it is characterised in that：Crucible material is aluminium oxide in step 1, and content is big
In 99%, constant weight is fired in 1300~1400 DEG C of electric furnace.
3. preparation method according to claim 1, it is characterised in that：Barium nitrate, calcium nitrate and nitric acid aluminum feedstock in step 1
Pureness specifications be chemistry it is pure；The mass concentration of prepared barium nitrate solution is 4~12%, and the mass concentration of calcium nitrate solution is
20~45%, the mass concentration of aluminum nitrate solution is 15~25%.
4. preparation method according to claim 1, it is characterised in that：Precipitating reagent in step 6 is by ammonium carbonate and ammonium hydroxide
It is 1.7~2.2 by weight:1 is dissolved in the mixed solution prepared after deionized water, wherein the mass concentration of ammonium hydroxide be 25~
28%；The mass concentration of ammonium carbonate is 10~25% in mixed solution.
5. preparation method according to claim 1, it is characterised in that：Precipitated product is BaCO in step 63、BaCa(CO3)2
With amorphous AOOH.
6. preparation method according to claim 1, it is characterised in that：The temperature of spray-wall interaction stove is 1250 in step 6
~1500 DEG C.
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| CN102354646A (en) * | 2011-09-23 | 2012-02-15 | 安徽华东光电技术研究所 | Preparation method of active substance for multi-injection cathode |
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| CN111115683A (en) * | 2020-01-17 | 2020-05-08 | 中国恩菲工程技术有限公司 | Device for preparing scandium-zirconium powder by coprecipitation coupling spray pyrolysis |
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