CN101575211A - High dense (SmxBa<1-x>)B6 polycrystalline block cathode and rapid preparation method thereof - Google Patents
High dense (SmxBa<1-x>)B6 polycrystalline block cathode and rapid preparation method thereof Download PDFInfo
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- CN101575211A CN101575211A CNA2009100868117A CN200910086811A CN101575211A CN 101575211 A CN101575211 A CN 101575211A CN A2009100868117 A CNA2009100868117 A CN A2009100868117A CN 200910086811 A CN200910086811 A CN 200910086811A CN 101575211 A CN101575211 A CN 101575211A
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Abstract
The invention discloses a (SmxBa<1-x>)B6 polycrystalline block cathode and a preparation method thereof, which pertain to technical field of rare-earth boride materials. The cathode material has the chemical composition of (SmxBa<1-x>)B6, wherein x is no less than 0.2 but no more than 1. The method comprises the steps of: respectively preparing nanometer power of SmH2 and BaH2 by adopting a direct current arc evaporation method; then mixing the nanometer power of SmH2 and BaH2 uniformly with raw material powder B by mixture ratio and then adopting a spark plasma reactive liquid sintering method under the conditions that the pressure ranges from 40 MPa to 70 MPa, the rate of temperature rise ranges from 90 DEG C per minute to 150 DEG C per minute and the sintering temperature ranges from 1300 DEG C to 1500 DEG C; and preserving the temperature for 5 minutes to 15 minutes, thus preparing single-phase dense (SmxBa<1-x>)B6. The invention has the advantages that the sintering temperature is low, the operation time is short and the process is simple.
Description
Technical field
The invention belongs to rare-earth boride material technology field, be specifically related to a kind of high densification (Sm
xBa
1-x) B
6Polycrystalline bulk cathode material and preparation method thereof.
Background technology
Rare-earth boride has a lot of outstanding physical and chemical performances, and especially lanthanum hexaborane has excellent electron emission characteristic, is widely used in various electronic cathode devices field.Along with the develop rapidly of electron beam and ion beam technology, more high performance requirement has been proposed relevant cathode material.The multicomponent rare earth boride negative electrode becomes research focus, (LaBa) B
6, (LaEu) B
6Deng cathode material be developed in succession (Liu Shuping, Yang Qingshan, Chen Weiping, Liu Jiaxiang, Li Zhonghua. rare metal and Wimet .2006,34 (3): 8-11).The traditional preparation process method of rare-earth boride generally was divided into for two steps: the first step adopts earlier methods such as boron heat, norbide reduction to prepare the multicomponent rare earth boride powder, with powder through chemical process removal of impurities purification, washing, drying, fragmentation, screening etc.; The method that second step was adopted solid state sintering again is under high temperature (1800 ℃～2100 ℃) condition, and long-time (2～10h) sintering prepare the multicomponent rare earth boride block materials.The shortcoming of these methods is that sintering temperature is too high, and sintering time is long, and product is fine and close inadequately, and product purity is not high, complex process, thereby can have a strong impact on the performance of product.
Summary of the invention
The objective of the invention is to solve prior art problems, and a kind of high densification (Sm is provided
xBa
1-x) B
6Polycrystalline bulk negative electrode and fast preparation method thereof.Method provided by the present invention has advantages such as sintering temperature is low, the time short, and technology is simple.
A kind of high densification (Sm provided by the present invention
xBa
1-x) B
6The chemical constitution of polycrystalline bulk negative electrode is (Sm
xBa
1-x) B
6, wherein, 0.2≤x≤1.
Method preparation (the Sm that the present invention adopts the direct current arc evaporative condenser to combine with the discharge plasma sintering reactive liquid sintering
xBa
1-x) B
6Polycrystalline bulk, concrete steps are as follows:
1) adopts the direct current arc evaporation condensing plant, be evacuated to 2.0 * 10
-2Behind the Pa, feeding volume ratio is (0～3): 1 hydrogen and argon gas, total gas pressure are 0.1MPa, are anode with elemental metals Sm piece, metal W is a negative electrode, and negative electrode and anodic distance are 2～4mm, and reaction current is 40～60A, response voltage is 30～50V, and the reaction times is 45min, prepares SmH
2Nanometer powder;
2) adopt the direct current arc evaporation condensing plant, be evacuated to 2.0 * 10
-2Behind the Pa, feeding volume ratio is (1～3): 1 hydrogen and argon gas, total gas pressure are 0.1MPa, are anode with elemental metals Ba piece, metal W is a negative electrode, and negative electrode and anodic distance are 2～4mm, and reaction current is 40～60A, response voltage is 30～50V, and the reaction times is 40min, prepares BaH
2Nanometer powder;
3) with SmH
2Nanometer powder, BaH
2In nanometer powder and the argon gas atmosphere of B powder below oxygen level is lower than 50ppm, press atomic ratio x: (1-x): 6 batchings, 0.2≤x≤1 wherein, grind mixing after, in the graphite jig of packing into;
4) graphite jig is placed the SPS sintering cavity, under the vacuum condition of 5Pa, be forced into 40～70Mpa after, be warming up to 1300～1500 ℃ of insulation 5～15min with the temperature rise rate of 90～150 ℃/min, cool to room temperature with the furnace, obtain (Sm
xBa
1-x) B
6The polycrystalline bulk negative electrode, wherein, 0.2≤x≤1 (principle is as shown in equation (1), (2) and (3)).
Wherein, described SmH
2The particle diameter of nanometer powder is 20～80nm; Described BaH
2The particle diameter of nanometer powder is 30～80nm.
xSmH
2(s)→xSm(s)+xH
2(g) (1)
(1-x)BaH
2(s)→(1-x)Ba(s)+(1-x)H
2(g) (2)
xSm(1)+(1-x)Ba(1)+6B(s)→(Sm
xBa
1-x)B
6(s) (3)
Compared with prior art, the present invention has following beneficial effect:
The inventive method sintering temperature is low, the time short, and technology is simple, prepared multicomponent rare earth boride (Sm
xBa
1-x) B
6Polycrystalline bulk material density height, the densification of scanning electron microscope analysis uniform crystal particles, relative density is after tested up to 99.41%, and Vickers' hardness reaches 2450Kg/mm
2, be the hexaboride pure phase through X-ray diffraction analysis.
Description of drawings
(the Sm of Fig. 1, embodiment 1 preparation
0.2Ba
0.8) B
6The X-ray spectrogram of polycrystalline bulk negative electrode.
(the Sm of Fig. 2, embodiment 1 preparation
0.2Ba
0.8) B
6The stereoscan photograph of polycrystalline bulk negative electrode
The SmB of Fig. 3, embodiment 3 preparations
6The X-ray spectrogram of polycrystalline bulk negative electrode.
The invention will be further described below in conjunction with the drawings and specific embodiments, but protection scope of the present invention is not limited to following embodiment.
Embodiment
Embodiment 1
1) adopts the direct current arc evaporation condensing plant, be evacuated to 2.0 * 10
-2Behind the Pa, the feeding volume ratio is 1: 1 hydrogen and an argon gas, and total gas pressure is 0.1MPa, is anode with elemental metals Sm piece, metal W is a negative electrode, and negative electrode and anodic distance are 2～4mm, and reaction current is 60A, response voltage is 30～50V, and the reaction times is 45min, prepares SmH
2Nanometer powder;
2) adopt the direct current arc evaporation condensing plant, be evacuated to 2.0 * 10
-2Behind the Pa, the feeding volume ratio is 1: 1 hydrogen and an argon gas, and total gas pressure is 0.1MPa, is anode with elemental metals Ba piece, metal W is a negative electrode, and negative electrode and anodic distance are 2～4mm, and reaction current is 60A, response voltage is 30～50V, and the reaction times is 40min, prepares BaH
2Nanometer powder;
3) with SmH
2Nanometer powder, BaH
2Nanometer powder and B powder are in the argon gas atmosphere of 10ppm in oxygen level, press 0.2: 0.8: 6 batching of atomic ratio, in the graphite jig of packing into behind the grinding mixing;
4) graphite jig is placed the SPS sintering cavity, under the vacuum condition of 5Pa, behind the pressurization 40Mpa, be warming up to 1300 ℃ of insulation 15min, cool to room temperature with the furnace, obtain (Sm with the temperature rise rate of 90 ℃/min
0.2Ba
0.8) B
6The polycrystalline bulk negative electrode.
Gained (Sm
0.2Ba
0.8) B
6Polycrystalline bulk negative electrode color is a canescence, and by XRD spectra (Fig. 1) as can be known, the sample principal phase is BaB
6, no dephasign, the Sm atom is solid-solubilized in the lattice, the unordered part of Ba atom that substituted.Scanning electron microscope analysis shows that crystal grain is tiny even, and densification physically well develops, and average grain size is about 0.5～3 μ m, as shown in Figure 2.Relative density reaches 98.77% through the test of Archimedes's drainage, and Vickers' hardness reaches 2116Kg/mm
2
Embodiment 2
1) adopts the direct current arc evaporation condensing plant, be evacuated to 2.0 * 10
-2Behind the Pa, feed argon gas, total gas pressure is 0.1MPa, is anode with elemental metals Sm piece, and metal W is a negative electrode, and negative electrode and anodic distance are 2～4mm, and reaction current is 50A, and response voltage is 30～50V, and the reaction times is 45min, prepares SmH
2Nanometer powder;
2) adopt the direct current arc evaporation condensing plant, be evacuated to 2.0 * 10
-2Behind the Pa, the feeding volume ratio is 3: 1 hydrogen and an argon gas, and total gas pressure is 0.1MPa, is anode with elemental metals Ba piece, metal W is a negative electrode, and negative electrode and anodic distance are 2～4mm, and reaction current is 40A, response voltage is 30～50V, and the reaction times is 40min, prepares BaH
2Nanometer powder;
3) with SmH
2Nanometer powder, BaH
2Nanometer powder and B powder are in the argon gas atmosphere of 20ppm in oxygen level, press 0.5: 0.5: 6 batching of atomic ratio, in the graphite jig of packing into behind the grinding mixing;
4) graphite jig is placed the SPS sintering cavity, under the vacuum condition of 5Pa, behind the pressurization 60Mpa, be warming up to 1400 ℃ of insulation 10min, cool to room temperature with the furnace, obtain (Sm with the temperature rise rate of 120 ℃/min
0.5Ba
0.5) B
6Polycrystalline bulk.
Gained (Sm
0.5Ba
0.5) B
6Polycrystalline bulk negative electrode color is a canescence, and by the X-ray diffraction spectrogram as can be known, the sample principal phase is BaB
6, no dephasign, the Sm atom is solid-solubilized in the lattice, the unordered part of Ba atom that substituted.Scanning electron microscope analysis shows the uniform crystal particles densification, physically well develops.Up to 99.37%, Vickers' hardness reaches 2434Kg/mm to relative density through the test of Archimedes's drainage
2
Embodiment 3
1) adopts the direct current arc evaporation condensing plant, be evacuated to 2.0 * 10
-2Behind the Pa, the feeding volume ratio is 3: 1 hydrogen and an argon gas, and total gas pressure is 0.1MPa, is anode with elemental metals Sm piece, metal W is a negative electrode, and negative electrode and anodic distance are 2～4mm, and reaction current is 40A, response voltage is 30～50V, and the reaction times is 45min, prepares SmH
2Nanometer powder;
2) with SmH
2Nanometer powder and B powder are in the argon gas atmosphere of 50ppm in oxygen level, press 1: 6 batching of atomic ratio, in the graphite jig of packing into behind the grinding mixing;
3) graphite jig is placed the SPS sintering cavity, under the vacuum condition of 5Pa, behind the pressurization 70Mpa, be warming up to 1500 ℃ of insulation 5min, cool to room temperature with the furnace, obtain SmB with the temperature rise rate of 150 ℃/min
6Polycrystalline bulk.
Gained SmB
6Polycrystalline bulk negative electrode color is blue, and by X-ray diffraction spectrogram (Fig. 3) as can be known, the sample principal phase is SmB
6Single-phase.Scanning electron microscope analysis shows the uniform crystal particles densification, physically well develops.Up to 99.41%, Vickers' hardness reaches 2450Kg/mm to relative density through the test of Archimedes's drainage
2
Claims (4)
1, a kind of (Sm
xBa
1-x) B
6The polycrystalline bulk negative electrode is characterized in that, the chemical constitution of described negative electrode is (Sm
xBa
1-x) B
6, wherein, 0.2≤x≤1.
2, the described a kind of (Sm of claim 1
xBa
1-x) B
6The preparation method of polycrystalline bulk is characterized in that, may further comprise the steps:
1) adopts the direct current arc evaporation condensing plant, be evacuated to 2.0 * 10
-2Behind the Pa, feeding volume ratio is (0～3): 1 hydrogen and argon gas, total gas pressure are 0.1MPa, are anode with elemental metals Sm piece, metal W is a negative electrode, and negative electrode and anodic distance are 2～4mm, and reaction current is 40～60A, response voltage is 30～50V, and the reaction times is 45min, prepares SmH
2Nanometer powder;
2) adopt the direct current arc evaporation condensing plant, be evacuated to 2.0 * 10
-2Behind the Pa, feeding volume ratio is (1～3): 1 hydrogen and argon gas, total gas pressure are 0.1MPa, are anode with elemental metals Ba piece, metal W is a negative electrode, and negative electrode and anodic distance are 2～4mm, and reaction current is 40～60A, response voltage is 30～50V, and the reaction times is 40min, prepares BaH
2Nanometer powder;
3) with SmH
2Nanometer powder, BaH
2In nanometer powder and the argon gas atmosphere of B powder below oxygen level is lower than 50ppm, press atomic ratio x: (1-x): 6 batchings, 0.2≤x≤1 wherein, grind mixing after, in the graphite jig of packing into;
4) graphite jig is placed the SPS sintering cavity, under the vacuum condition of 5Pa, be forced into 40～70Mpa after, be warming up to 1300～1500 ℃ of insulation 5～15min with the temperature rise rate of 90～150 ℃/min, cool to room temperature with the furnace, obtain (Sm
xBa
1-x) B
6The polycrystalline bulk negative electrode, wherein, 0.2≤x≤1.
3, method according to claim 2 is characterized in that, described SmH
2The particle diameter of nanometer powder is 20～80nm.
4, method according to claim 2 is characterized in that, described BaH
2The particle diameter of nanometer powder is 30～80nm.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103601207A (en) * | 2013-11-12 | 2014-02-26 | 北京工业大学 | Preparation method of high-purity high-density YbB6 polycrystal blocky negative electrode material |
| CN104831352A (en) * | 2015-04-08 | 2015-08-12 | 井冈山大学 | High-purity high-compactness (LaxSm1-x)B6 polycrystalline cathode material and preparation method thereof |
| CN107863412A (en) * | 2017-10-20 | 2018-03-30 | 北京大学 | Photodetector and method of manufacturing the same |
-
2009
- 2009-06-05 CN CNA2009100868117A patent/CN101575211A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103601207A (en) * | 2013-11-12 | 2014-02-26 | 北京工业大学 | Preparation method of high-purity high-density YbB6 polycrystal blocky negative electrode material |
| CN104831352A (en) * | 2015-04-08 | 2015-08-12 | 井冈山大学 | High-purity high-compactness (LaxSm1-x)B6 polycrystalline cathode material and preparation method thereof |
| CN107863412A (en) * | 2017-10-20 | 2018-03-30 | 北京大学 | Photodetector and method of manufacturing the same |
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Open date: 20091111 |