CN103700561B - Active composition for barium-tungsten cathode, preparation method thereof and preparation method of barium-tungsten cathode - Google Patents
Active composition for barium-tungsten cathode, preparation method thereof and preparation method of barium-tungsten cathode Download PDFInfo
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Abstract
The invention discloses an active composition for a barium-tungsten cathode, a preparation method thereof and a preparation method of the barium-tungsten cathode. The active composition for the barium-tungsten cathode comprises barium carbonate, calcium carbonate and aluminum powder, wherein 100 parts by weight of calcium carbonate is taken as a reference, the content of barium carbonate can be 1200-1500 parts by weight, and the content of aluminum powder can be 80-140 parts by weight; preferably, the content of barium carbonate is 1360-1410 parts by weight and the content of aluminum powder is 100-120 parts by weight based on 100 parts by weight of calcium carbonate. The invention optimizes the proportion of barium carbonate, calcium carbonate and aluminum powder, simplifies the preparation method of the barium-tungsten cathode active substance and the preparation process of the tungsten-barium cathode, improves the current emission capability of the aluminate barium-tungsten cathode, and reduces the process difficulty and cost.
Description
Technical field
The present invention relates to barium-tungsten dispense cathode field, particularly, relate to a kind of combination of the activity for barium-tungsten dispense cathodeThe preparation method of thing and preparation method thereof and barium-tungsten dispense cathode.
Background technology
Microwave vacuum device is in Modern Satellite communication, satellite navigation, especially at military electronics equipment as electronicsIn jamming equipment, prior-warning plane, fire control radar, accurate guidance, day by day demonstrate the effect of not replacing.As " heart " of microwave vacuum device, the raising in emission of cathode ability and life-span, with microwave electrovacuumThe upgrading of device, particularly military device, regenerate closely related. Because along with the work of microwave vacuum deviceThe raising of frequency, its electronic efficiency can decline rapidly, therefore needs to improve the emissivities of negative electrode. At bariumIn tungsten cathode, the height of the quality of active material is the key factor that determines emission of cathode performance quality. DifferentMaximum emission current, evaporation rate, stability and the anti-poisoning performance of the active material of formula all haveVery large difference. In the prior art, be all generally adopt first by brium carbonate, calcium carbonate and aluminium oxide byCertain proportion high temperature sintering becomes aluminate, and then in hydrogen stove, high-temperature heating aluminate makes it melt to soak poolSpongy body of tungsten, thus prepare aluminate barium-tungsten dispense cathode, the above-mentioned method step of preparing aluminate barium-tungsten dispense cathodeLoaded down with trivial details, consumed energy is more, and the maximum emission current of the tungsten barium negative electrode making is also not high, instituteTo seek the higher technique of maximum emission current of the tungsten barium negative electrode that a kind of step makes simply simultaneouslyIt is the problem that this area is needed solution badly.
Summary of the invention
The object of the invention is in prior art, to prepare tungsten barium negative electrode loaded down with trivial details while of method barium tungsten in order to overcomeThe formula of the active material in negative electrode can not make the defect of high-quality tungsten barium negative electrode, and a kind of high-quality is providedThe active compound for barium-tungsten dispense cathode and preparation method thereof simple with step, make emission maximum electric currentThe preparation method of the barium-tungsten dispense cathode that density is higher.
To achieve these goals, the invention provides a kind of combination of the activity for barium-tungsten dispense cathode structureThing, wherein, described composition contains brium carbonate, calcium carbonate and aluminium powder, and described composition contains carbonic acidBarium, calcium carbonate and aluminium powder, taking the calcium carbonate of 100 weight portions as benchmark, the content of brium carbonate is1200-1500 weight portion, the content of aluminium powder is 80-140 weight portion; Preferably, with 100 weight portionsCalcium carbonate is benchmark, and the content of brium carbonate is 1360-1410 weight portion, and the content of aluminium powder is 100-120Weight portion.
The present invention also provides a kind of preparation method of the active compound for barium-tungsten dispense cathode structure, itsIn, described method comprises that brium carbonate, calcium carbonate and aluminium powder being mixed and be ground to particle diameter is 1-10 μ m,Taking the calcium carbonate of 100 weight portions as benchmark, the consumption of brium carbonate is 1200-1500 weight portion, aluminium powderConsumption is 80-140 weight portion; Preferably, taking the calcium carbonate of 100 weight portions as benchmark, brium carbonateConsumption is 1360-1410 weight portion, and the consumption of aluminium powder is 100-120 weight portion.
The present invention also provides make according to above-mentioned composition and according to above-mentioned method describedThe application preparation method of composition in a kind of barium tungsten impregnated cathode structure, wherein, the method comprises:
The spongy body of tungsten that is placed in cathode cup is carried out to the first heat treatment cooling;
Active material is covered to surface the compacting through heat treated spongy body of tungsten, and carry out the second heatProcess also cooling;
Described active material is above-mentioned for the active compound of barium-tungsten dispense cathode or by above-mentioned methodThe active compound for barium-tungsten dispense cathode preparing.
The present invention, by the optimization of the proportioning to brium carbonate, calcium carbonate and aluminium powder, simplifies barium-tungsten dispense cathode simultaneouslyThe preparation process of the preparation method of active material and tungsten barium negative electrode, has improved the electric current of aluminate barium-tungsten dispense cathodeEmissivities, also reduce technology difficulty and cost simultaneously.
Other features and advantages of the present invention are described in detail the detailed description of the invention part subsequently.
Brief description of the drawings
Accompanying drawing is to be used to provide a further understanding of the present invention, and forms a part for description, withDetailed description of the invention one is below used from explanation the present invention, but is not construed as limiting the invention. ?In accompanying drawing:
Fig. 1 is that the active material of tungsten barium cathode surface of preparation in embodiment 1 is after the second heat treatmentXRD diffraction pattern; And
Fig. 2 is the schematic diagram of measuring the maximum emission current of tungsten barium negative electrode.
Detailed description of the invention
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is elaborated. Should be understood that,Detailed description of the invention described herein only, for description and interpretation the present invention, is not limited to thisBright.
The invention provides a kind of active compound for barium-tungsten dispense cathode, wherein, described composition containsBrium carbonate, calcium carbonate and aluminium powder, taking the calcium carbonate of 100 weight portions as benchmark, the content of brium carbonate canFor 1200-1500 weight portion, the content of aluminium powder can be 80-140 weight portion; Preferably, with 100 weightThe calcium carbonate of part is benchmark, and the content of brium carbonate is 1360-1410 weight portion, and the content of aluminium powder is100-120 weight portion.
The formula of the active compound for barium-tungsten dispense cathode provided by the invention directly adopts aluminium powder conductA wherein component, highly purified aluminium powder (purity is 99.99%) is extremely easy to get, and impure amount is few, rightThe quality that makes tungsten barium negative electrode plays vital effect, and the proportioning of each component is more reasonable simultaneously, systemGet impurity residual after tungsten barium negative electrode few.
In above-mentioned active compound, the particle size of each component has range of choice very widely, preferablyGround, the particle diameter of described composition is 1-10 μ m, adopts the particle of micron level, more can make in systemIn the standby process of tungsten barium negative electrode, each component more easy-sintering enters in tungsten barium negative electrode.
The present invention also provides a kind of preparation method of the active compound for barium-tungsten dispense cathode, wherein, and instituteThe method of stating comprises mixes brium carbonate, calcium carbonate and aluminium powder grind, with the calcium carbonate of 100 weight portionsFor benchmark, the consumption of brium carbonate is 1200-1500 weight portion, and the consumption of aluminium powder is 80-140 weight portion;Preferably, taking the calcium carbonate of 100 weight portions as benchmark, the consumption of brium carbonate is 1360-1410 weight portion,The consumption of aluminium powder is 100-120 weight portion.
In said method, preferably, it is 1-10 μ m that the condition of grinding makes the particle diameter of the composition obtaining.
In said method, preferably, described method is also included in brium carbonate, calcium carbonate and aluminium powder mixedBefore merging grinding, calcium carbonate and brium carbonate are dried to 20-30h at 180-200 DEG C, are preferably 24h, thisBe in brium carbonate, calcium carbonate and aluminium powder, contain moisture and the activity that causes active compound notHigh.
In said method, the order by merging of described brium carbonate, calcium carbonate and aluminium powder is not particularly limited, bothCan be to be mixed together, can be also to mix in order. For example, first mixed carbonic acid barium and calcium carbonate add againEnter aluminium powder and mix, but the quality of the active material that order by merging makes for the present invention affects notGreatly.
The present invention also provides a kind of preparation method of barium-tungsten dispense cathode, and wherein, the method comprises: will be placed inSpongy body of tungsten in cathode cup carries out the first heat treatment cooling; Active material is covered through Overheating TreatmentSurface the compacting of spongy body of tungsten, and carry out the second heat treatment cooling; Described active material is above-mentionedPrepare for the active compound of barium-tungsten dispense cathode or by above-mentioned method for barium-tungsten dispense cathodeActive compound. Adopt two step heat-treating methods to produce tungsten barium negative electrode, step is simple, makes simultaneouslyThe maximum emission current of tungsten barium negative electrode is large.
The first described heat treated object, in order to shrink the porosity of spongy body of tungsten, has reached tungsten simultaneouslyCavernous body carries out the effect of exhaust and purification, and the first heat treatment can be both that a step intensification also can adopt progressivelyIntensification is processed, and preferably, adopts the heat-treating methods progressively heating up, and comprising: will accommodate tungstenThe cathode cup of cavernous body is placed in molybdenum boat, and molybdenum boat is placed in to hydrogen stove, the first intensification speed with 3-4 DEG C/minDegree is warming up to 200-250 DEG C, and then is warming up to 1200-1600 DEG C with the programming rate of 22-37 DEG C/min,And be incubated 5-20 minute.
Cooling means after the first heat treatment and condition are the conventional sides that use of those skilled in the artMethod and condition, for example, naturally cooling, cooling temperature is generally room temperature as 20-30 DEG C.
Described the second heat treatment is by active material sintering and soaks pool and enter in spongy body of tungsten, thereby obtains toolThere is the tungsten barium electrode of current emission ability. Under preferable case, the second heat treatment adopts the heat place of progressively heating upThe method of reason, the method comprises: the cathode cup that accommodates the spongy body of tungsten that covers active material is placed in to molybdenumIn boat, molybdenum boat is placed in to hydrogen stove, under the existence of hydrogen, heat-treats, described heat treated processComprise: be first warming up to 1200-1300 DEG C with the programming rate of 390-640 DEG C/min, and be incubated 5-15 and divideClock, and then be warming up to 1700-1800 DEG C with the programming rate of 265-600 DEG C/min, and be incubated 1-3 and divideClock.
Cooling means after the second heat treatment and condition are the conventional sides that use of those skilled in the artMethod and condition, for example, naturally cooling, cooling temperature is generally room temperature as 20-30 DEG C.
According to the present invention, the flow of the hydrogen in described the first heat treatment and the second heat treatment is as long as ensure instituteState heat treatment in hydrogen atmosphere, for example, the flow of described hydrogen can be80-120L/min. In addition, well known to a person skilled in the art to be, in order to prevent hydrogen stove in useBlast, conventionally before passing into hydrogen by hydrogen stove evacuation to discharge air, described in the bar that vacuumizesIt is 5-15Pa that part is generally vacuum.
In the preparation method of above-mentioned tungsten barium negative electrode, the model selected of the mass ratio of spongy body of tungsten and active materialEnclose widelyr, can save again active matter in order to obtain the tungsten barium negative electrode that maximum emission current is largeMatter, avoids causing waste, preferably, and with respect to the spongy body of tungsten of 100 weight portions, active materialConsumption be 10-12 weight portion.
In addition, above-mentioned active material is covered to surface the side of compacting through heat treated spongy body of tungstenMethod is conventionally known to one of skill in the art, makes active material be attached to the surface of spongy body of tungsten as long as ensureCan't overflow cathode cup.
Above-mentioned spongy body of tungsten can form by the mode of compacting, for example, can be in hydraulic press orDirectly in cathode cup, suppress W-Re mixture and obtain spongy body of tungsten. Described W-Re mixture be by tungsten powder andAfter the mixing of rhenium powder ball milling, obtain. Under preferable case, taking the tungsten powder of 100 weight portions as benchmark, rhenium powderConsumption is 300-550 weight portion; Preferably, taking the tungsten powder of 100 weight portions as benchmark, the consumption of rhenium powderFor 380-430 weight portion. The size of pressure directly determines the height of the quality of spongy body of tungsten, spongy body of tungstenThe shaky emission current that is unfavorable for of compacting, pressure causes too greatly the space of spongy body of tungsten too little, is unfavorable forIn second step heat treatment process, active material enters in spongy body of tungsten, preferably, described spongy body of tungsten be0.5-1.5Mpa, the porous base obtaining after more preferably under 0.9-1.1Mpa pressure, W-Re mixture being suppressedBody. Therefore the porosity that, presses down in above-mentioned preferred condition the spongy body of tungsten making is 25-35%.
Below by specific embodiment, the invention will be further described:
In following embodiment and comparative example, the purity of tungsten powder used is 99.99%, and the purity of rhenium powder is99.99%, the purity of aluminium powder is 99.99%.
Embodiment 1
The preparation of active material: take 25g brium carbonate and 10g calcium carbonate, place it in porcelain cup separatelyIn; The cup that brium carbonate and calcium carbonate are housed is respectively placed in drying cupboard, at 180 DEG C, is dried 24Hour. With the byssus cleaning mortar that dips in alcohol, pestle and perching knife; On assay balance, weigh with pan paperDried brium carbonate 6.9g, dried calcium carbonate 0.5g and aluminium powder 0.54g; By load weighted chemistryMaterial is poured in mortar by the order of brium carbonate, calcium carbonate, aluminium powder; Stir the mixture 1 minute with perching knife;With pestle milled mixtures 30 minutes; Ground just obtain active compound A1(composition particle diameter be 5 μ m),And pour in the weighing cup of frosted plug stand-byly, put rubber and stick explanation mixture composition and dateLabel, be generally no more than 3 months memory time, otherwise the activity of active material will reduce greatly.
The first heat treatment: the W-Re mixture mixing (is got to tungsten powder and 80 weight portions of 20 weight portionsRhenium powder mix and ball grinding stirring) be placed in the cathode cup of molybdenum matter and press under the pressure of 1.0MpaMake spongy body of tungsten (porosity 30%), and the cathode cup that contains spongy body of tungsten is placed in to molybdenum boat entersRow heat treatment, detailed process is: be first evacuated to 10Pa and discharge air, then pass into hydrogen, hydrogenThe flow of stream is 100L/min, in 60 minutes, is warming up to 230 DEG C from 20 DEG C; Continue to heat up, 40In minute, be warming up to 1500 DEG C and be incubated 10 minutes from 230 DEG C; With hydrogen stove cooling down 15 minutes to 20DEG C, and take out spongy body of tungsten.
The second heat treatment: the above-mentioned active material preparing is poured into and suppressed the surface of spongy body of tungsten and pressReal, make the surface of the active mixture after compacting and the edge of cathode cup on a horizontal plane or lower thanThis horizontal plane 0.1-0.2mm; With the outer surface of the clean cathode cup of brush, unnecessary active material is removed,With respect to the spongy body of tungsten of 100 weight portions, the consumption of active material is 10 weight portions. And will accommodateCompacting has the cathode cup of the spongy body of tungsten of active material to put into molybdenum boat, then puts into drying bottle for subsequent use.The molybdenum boat that cathode cup is housed is put into hydrogen stove, hydrogen burner hearth is evacuated to 10Pa with forepump, andMaintain this vacuum 10 minutes; Close vacuum valve, close forepump, logical hydrogen, sets hydrogenFlow 100L/min, purifies burner hearth 5-6 minute; Check hydrogen purity, light hydrogen opening hydrogen, checkHydrogen leak source temperature; To the hydrogen stove heat temperature raising of negative electrode is housed, soak damp spongy body of tungsten. Concrete temperature-rise periodAs follows: to continue, in hydrogen atmosphere, in 3 minutes, temperature to be risen to 1270 DEG C from 20 DEG C; Insulation 9Minute; Continue to heat up, in 1.5 minutes, be warming up to 1760 DEG C from 1270 DEG C; Be incubated 70 seconds; With stoveCooling down 10 minutes to 20 DEG C; Close hydrogen and import and export, hydrogen stove burner hearth is vacuumized, be evacuated to pressureFor 10Pa, then close forepump; To the venting of hydrogen stove, take out negative electrode and use microscopic examination negative electrodeDipping situation, soaking negative electrode after salt, on the back of spongy body of tungsten and the surface of emission, can to form some grey semi-transparentBright glass substance B 1. This substance B 1 is carried out to XRD analysis, obtain XRD as shown in Figure 1Figure, the corresponding angle of diffraction that obtains significant peak is respectively: 21.98 °, 31.30 °, 38.6 °, 44.88°, 50.50 ° and 55.72 °.
The above-mentioned tungsten barium negative electrode that makes is packed in electron gun and detected, and it is former that Fig. 2 is that target detectsReason schematic diagram, the negative electrode in figure is tungsten barium negative electrode, the electronics that the emission of cathode of tungsten barium goes out is by the collection in figureThe utmost point is collected, and emission of cathode region sectional dimension is 0.14mm × 2.5mm, and computing formula is:
Because the cathode current emission IkRelevant with the accelerating potential Ua between negative electrode and anode, can be along with addingSpeed voltage UaIncrease and increase, but just can be again along with accelerating potential U in the time increasing to certain valuea'sIncrease and increase, but remain on a relatively stable value, the emission maximum electric current I that this value is negative electrodek。Thereby the maximum emission current that is calculated tungsten barium negative electrode by above-mentioned formula is 70A/cm2。
Embodiment 2
Prepare active material, spongy body of tungsten and barium-tungsten dispense cathode, the present embodiment according to the method for embodiment 1, in the preparation process of active material, to pour the matter of each component in mortar into embodiment 1 differenceAmount changes, brium carbonate 6.9g, and calcium carbonate 0.5g and aluminium powder 0.6g, the present embodiment makes active combinationThing A2(composition particle diameter be 9 μ m), after the second heat treatment, obtain the thing of grey translucent glass shapeMatter B2. B2 is through XRD analysis, and the corresponding angle of diffraction that obtains significant peak is respectively: 21.98°, 31.30 °, 38.6 °, 44.88 °, 50.50 ° and 55.72 °. Tungsten barium the moon in the present embodimentThe maximum emission current of the utmost point is 68A/cm2。
Embodiment 3
Prepare active material, spongy body of tungsten and barium-tungsten dispense cathode, the present embodiment according to the method for embodiment 1, in the preparation process of active material, to pour the matter of each component in mortar into embodiment 1 differenceAmount changes, brium carbonate 6.9g, and calcium carbonate 0.5g and aluminium powder 0.5g, the present embodiment makes active combinationThing A3(composition particle diameter be 3 μ m), after the second heat treatment, obtain the thing of grey translucent glass shapeMatter B3. B3 is through XRD analysis, and the corresponding angle of diffraction that obtains significant peak is respectively: 21.98°, 31.30 °, 38.6 °, 44.88 °, 50.50 ° and 55.72 °. Tungsten barium the moon in the present embodimentThe maximum emission current of the utmost point is 69A/cm2。
Embodiment 4
Prepare active material, spongy body of tungsten and barium-tungsten dispense cathode, the present embodiment according to the method for embodiment 1, in the preparation process of active material, to pour the matter of each component in mortar into embodiment 1 differenceAmount changes, brium carbonate 7.05g, and calcium carbonate 0.5g and aluminium powder 0.54g, the present embodiment makes active groupCompound A4(composition particle diameter be 5 μ m), after the second heat treatment, obtain grey translucent glass shapeSubstance B 4. B4 is through XRD analysis, and the corresponding angle of diffraction that obtains significant peak is respectively: 21.98°, 31.30 °, 38.6 °, 44.88 °, 50.50 ° and 55.72 °. Tungsten barium the moon in the present embodimentThe maximum emission current of the utmost point is 67A/cm2。
Embodiment 5
Prepare active material, spongy body of tungsten and barium-tungsten dispense cathode, the present embodiment according to the method for embodiment 1, in the preparation process of active material, to pour the matter of each component in mortar into embodiment 1 differenceAmount changes, brium carbonate 6.8g, and calcium carbonate 0.5g and aluminium powder 0.54g, the present embodiment makes active groupCompound A5(composition particle diameter be 5 μ m), after the second heat treatment, obtain grey translucent glass shapeSubstance B 5. B5 is through XRD analysis, and the corresponding angle of diffraction that obtains significant peak is respectively: 21.98°, 31.30 °, 38.6 °, 44.88 °, 50.50 ° and 55.72 °. Tungsten barium the moon in the present embodimentThe maximum emission current of the utmost point is 68A/cm2。
Embodiment 6
Prepare active material, spongy body of tungsten and barium-tungsten dispense cathode, the present embodiment according to the method for embodiment 1, in the preparation process of active material, to pour the matter of each component in mortar into embodiment 1 differenceAmount changes, brium carbonate 6.0g, and calcium carbonate 0.5g and aluminium powder 0.7g, the present embodiment makes active combinationThing A6(composition particle diameter be 5 μ m), after the second heat treatment, obtain the thing of grey translucent glass shapeMatter B6. B6 is through XRD analysis, and the corresponding angle of diffraction that obtains significant peak is respectively: 21.98°, 31.30 °, 38.6 °, 44.88 °, 50.50 ° and 55.72 °. Tungsten barium the moon in the present embodimentThe maximum emission current of the utmost point is 60A/cm2。
Embodiment 7
Prepare active material, spongy body of tungsten and barium-tungsten dispense cathode, the present embodiment according to the method for embodiment 1, in the preparation process of active material, to pour the matter of each component in mortar into embodiment 1 differenceAmount changes, brium carbonate 7.5g, and calcium carbonate 0.5g and aluminium powder 0.4g, the present embodiment makes active combinationThing A7(composition particle diameter be 5 μ m), after the second heat treatment, obtain the thing of grey translucent glass shapeMatter B7. B7 is through XRD analysis, and the corresponding angle of diffraction that obtains significant peak is respectively: 21.98°, 31.30 °, 38.6 °, 44.88 °, 50.50 ° and 55.72 °. Tungsten barium the moon in the present embodimentThe maximum emission current of the utmost point is 62A/cm2。
Embodiment 8
Prepare active material, spongy body of tungsten and barium-tungsten dispense cathode, the present embodiment according to the method for embodiment 1That the temperature in the concrete temperature-rise period in the second heat treated process has been done with embodiment 1 differenceChange, concrete temperature-rise period is as follows:
In 3 minutes, temperature is risen to 1210 DEG C from 20 DEG C; Be incubated 9 minutes; Continue to heat up, 1.5In minute, be warming up to 1700 DEG C from 1210 DEG C; Be incubated 70 seconds; With stove cooling down 10 minutes to 20 DEG C;Close hydrogen and import and export, hydrogen stove burner hearth is vacuumized, being evacuated to pressure is 10Pa, then closes fore vacuumPump; To the venting of hydrogen stove, take out negative electrode and use microscopic examination cathode dipping situation, the negative electrode soaking after salt existsOn the back of spongy body of tungsten and the surface of emission, can form the material of some grey translucent glass shapes.
The present embodiment make active compound A8(composition particle diameter be 9 μ m), after the second heat treatmentObtain the substance B 8 of grey translucent glass shape. B8 is through XRD analysis, obtains significant peakThe corresponding angle of diffraction is respectively: 21.98 °, 31.30 °, 38.6 °, 44.88 °, 50.50 ° and 55.72°. The maximum emission current of the tungsten barium negative electrode in the present embodiment is 61A/cm2。
Embodiment 9
Prepare active material, spongy body of tungsten and barium-tungsten dispense cathode, the present embodiment according to the method for embodiment 1To take a step in the concrete temperature-rise period in process prepared by tungsten barium negative electrode with embodiment 1 differenceThe mode heating up, concrete temperature-rise period is as follows:
In 4.5 minutes, temperature is risen to 1700 DEG C from 20 DEG C; Be incubated 10 minutes; With stove cooling down10 minutes to 20 DEG C; Close hydrogen and import and export, hydrogen stove burner hearth is vacuumized, being evacuated to pressure is 10Pa,Then close forepump; To the venting of hydrogen stove, take out negative electrode and use microscopic examination cathode dipping situation,Soak negative electrode after salt and can form some grey translucent glass shapes on the back of spongy body of tungsten and the surface of emissionMaterial.
The present embodiment make active compound A9(composition particle diameter be 9 μ m), after the second heat treatmentObtain the substance B 9 of grey translucent glass shape. B9 is through XRD analysis, obtains significant peakThe corresponding angle of diffraction is respectively: 21.98 °, 31.30 °, 38.6 °, 44.88 °, 50.50 ° and 55.72°. The maximum emission current of the tungsten barium negative electrode in the present embodiment is 45A/cm2。
Comparative example 1
Prepare active material, spongy body of tungsten and barium-tungsten dispense cathode, this comparative example according to the method for embodiment 1With embodiment 1 difference be, pour the quality of each component in mortar into and change, brium carbonate 8.0g,Calcium carbonate 0.5g and aluminium powder 0.54g, the present embodiment make active compound C1(composition particle diameter be 5 μ m),After the second heat treatment, obtain the material D1 of grey translucent glass shape. D1 process XRD analysis,The corresponding angle of diffraction that obtains significant peak is respectively: 21.98 °, 31.30 °, 38.6 °, 44.88°, 50.50 ° and 55.72 °. The maximum emission current of the tungsten barium negative electrode in the present embodiment is 35A/cm2。
Comparative example 2
Prepare active material, spongy body of tungsten and barium-tungsten dispense cathode, this comparative example according to the method for embodiment 1With embodiment 1 difference be, pour the quality of each component in mortar into and change, brium carbonate 5.5g,Calcium carbonate 0.5g and aluminium powder 0.54g, the present embodiment make active compound C2(composition particle diameter be 5 μ m),After the second heat treatment, obtain the material D2 of grey translucent glass shape. D2 process XRD analysis,The corresponding angle of diffraction that obtains significant peak is respectively: 21.98 °, 31.30 °, 38.6 °, 44.88°, 50.50 ° and 55.72 °. The maximum emission current of the tungsten barium negative electrode in the present embodiment is 34A/cm2。
Comparative example 3
Prepare active material, spongy body of tungsten and barium-tungsten dispense cathode, this comparative example according to the method for embodiment 1With embodiment 1 difference be, pour the quality of each component in mortar into and change, brium carbonate 6.9g,Calcium carbonate 0.5g and aluminium powder 0.35g, the present embodiment make active compound C3(composition particle diameter be 5 μ m),After the second heat treatment, obtain the material D3 of grey translucent glass shape. D3 process XRD analysis,The corresponding angle of diffraction that obtains significant peak is respectively: 21.98 °, 31.30 °, 38.6 °, 44.88°, 50.50 ° and 55.72 °. The maximum emission current of the tungsten barium negative electrode in the present embodiment is31A/cm2。
Comparative example 4
Prepare active material, spongy body of tungsten and barium-tungsten dispense cathode, this comparative example according to the method for embodiment 1With embodiment 1 difference be, pour the quality of each component in mortar into and change, brium carbonate 6.9g,Calcium carbonate 0.5g and aluminium powder 0.72g, the present embodiment make active compound C4(composition particle diameter be 5 μ m),After the second heat treatment, obtain the material D4 of grey translucent glass shape. D4 process XRD analysis,The corresponding angle of diffraction that obtains significant peak is respectively: 21.98 °, 31.30 °, 38.6 °, 44.88°, 50.50 ° and 55.72 °. The maximum emission current of the tungsten barium negative electrode in the present embodiment is33A/cm2。
Learn by retrieval, in XRD diffraction pattern, the corresponding angle of diffraction at significant peak is respectively: 21.98°, the material of 31.30 °, 38.6 °, 44.88 °, 50.50 ° and 55.72 ° is2.4BaO0.6CaOAl2O3. Known by embodiment 1-9 and comparative example 1-4, in embodiment and contrastIn example, make tungsten barium electrode and be barium aluminate tungsten barium electrode. The maximum of barium aluminate tungsten barium electrode in prior artCurrent emission density is 30A/cm2, and the formula of the active compound in embodiment 1-5 is of the present invention excellentSelect scope, the maximum emission current of the tungsten barium negative electrode making is close to 70A/cm2, be prior artIn with the maximum emission current of eka-tungsten barium electrode more than 1.5 times; Activity combination in embodiment 6-7The formula of thing is not preferred scope of the present invention, and the maximum emission current of the tungsten barium negative electrode making approachesIn 60A/cm2; The performance that the tungsten barium electrode that preferable range obtains is described is better; In embodiment 9 secondThe method that heat treatment adopts a step to heat up, the maximum emission current of the tungsten barium electrode making is 45A/cm2, illustrate and adopt preferred the second heat treatment mode can make tungsten barium electrode there is better performance;From comparative example 1-4, the formula of active compound is within the scope of the invention time, the tungsten barium makingThe emission maximum current capacity of negative electrode is poor, although effect compared with prior art quite or slightly high obviously lowThereby the performance that makes tungsten barium electrode in embodiment 1-7 illustrates superiority of the present invention.
Below describe by reference to the accompanying drawings the preferred embodiment of the present invention in detail, still, the present invention does not limitDetail in above-mentioned embodiment, within the scope of technical conceive of the present invention, can be to the present inventionTechnical scheme carry out multiple simple variant, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition each the concrete technology spy described in above-mentioned detailed description of the inventionLevy, in reconcilable situation, can combine by any suitable mode, for fear of needn'tThe repetition of wanting, the present invention is to the explanation no longer separately of various possible combinations.
In addition, between various embodiment of the present invention, also can be combined, as long as itsWithout prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (8)
1. a preparation method for barium-tungsten dispense cathode, is characterized in that, the method comprises:
The spongy body of tungsten that is placed in cathode cup is carried out to the first heat treatment cooling;
Active material is covered to surface the compacting through heat treated spongy body of tungsten, and carry out the second heatProcess also cooling;
Wherein, described the first heat-treating methods comprises: the cathode cup that accommodates spongy body of tungsten is placed in to molybdenumIn boat, molybdenum boat is placed in to hydrogen stove, under the existence of hydrogen, heat-treats, described heat treated processComprise: be first warming up to 200-250 DEG C with the programming rate of 3-4 DEG C/min, and then with 22-37 DEG C/minProgramming rate be warming up to 1200-1600 DEG C, and be incubated 5-20 minute; Described the second heat-treating methodsComprise: the cathode cup that accommodates the spongy body of tungsten that covers active material is placed in to molybdenum boat, molybdenum boat is placed inIn hydrogen stove, under the existence of hydrogen, heat-treat, described heat treated process comprises: first withThe programming rate of 390-640 DEG C/min is warming up to 1200-1300 DEG C, and is incubated 5-15 minute, and thenProgramming rate with 265-600 DEG C/min is warming up to 1700-1800 DEG C, and is incubated 1-3 minute; Described workProperty material contains brium carbonate, calcium carbonate and aluminium powder, taking the calcium carbonate of 100 weight portions as benchmark, and carbonic acidThe content of barium is 1200-1500 weight portion, and the content of aluminium powder is 80-140 weight portion; Described active materialParticle diameter be 1-10 μ m.
2. preparation method according to claim 1, taking the calcium carbonate of 100 weight portions as benchmark,The content of brium carbonate is 1360-1410 weight portion, and the content of aluminium powder is 100-120 weight portion.
3. preparation method according to claim 1, is characterized in that, described active material passes throughBrium carbonate, calcium carbonate and aluminium powder are mixed and grind and make.
4. preparation method according to claim 3, wherein, described active material passes through carbonic acidBarium, calcium carbonate and aluminium powder mix and make, and before grinding by calcium carbonate and brium carbonate at 180-200 DEG CDry 20-30h down.
5. preparation method according to claim 4, wherein, described active material passes through carbonic acidBarium, calcium carbonate and aluminium powder mix and make, and before grinding by calcium carbonate and brium carbonate at 180-200 DEG CDry 24h down.
6. according to the method described in any one in claim 1-5, wherein, with respect to 100 weightThe spongy body of tungsten of part, the consumption of active material is 10-12 weight portion.
7. according to the method described in any one in claim 1-5, wherein, described spongy body of tungsten isThe porous matrix obtaining after W-Re mixture being suppressed under 0.5-1.5Mpa pressure, the hole of porous matrixRate is 25-35%; Described W-Re mixture is for tungsten powder and the mixing of rhenium powder are also obtained after ball milling, with 100The tungsten powder of weight portion is benchmark, and the consumption of rhenium powder is 300-550 weight portion.
8. method according to claim 7, wherein, taking the tungsten powder of 100 weight portions as benchmark,The consumption of rhenium powder is 380-430 weight portion.
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