CN101434395B - Multicomponent rare earth boride (CexBa1-x)B6 and preparation thereof - Google Patents
Multicomponent rare earth boride (CexBa1-x)B6 and preparation thereof Download PDFInfo
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- CN101434395B CN101434395B CN2008102393866A CN200810239386A CN101434395B CN 101434395 B CN101434395 B CN 101434395B CN 2008102393866 A CN2008102393866 A CN 2008102393866A CN 200810239386 A CN200810239386 A CN 200810239386A CN 101434395 B CN101434395 B CN 101434395B
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- earth boride
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Abstract
The invention relates to a polynary rare earth boride (CexBa<1-x>)B6 polycrystal block material and a preparation method thereof, which pertain to the technical field of rare earth boride materials. The polynary rare earth boride has high research and application values, but currently, research on the polynary rare earth boride is less and the preparation technology is complex. The composition ofthe material is (CexBa<1-x>)B6, wherein, x is less than or equal to 0.8 and more than or equal to 0.2. In the invention, CeH2 and BaH2 nanometer powders are respectively prepared by adopting a directcurrent arc evaporation method and then mixed with material B powders in protective atmosphere, and by adopting a discharge plasma sintering technology, the polynary rare earth boride (CexBa<1-x>)B6 block material is prepared under the conditions of pressure of 30 to 60MPa, heating rate of 120 to 160 DEG C per minute, sintering temperature of 1400 to 1600 DEG C and heat preservation of 5 to 15min. The method has low sintering temperature, short time and simple process, and the prepared (CexBa<1-x>)B6 is high-purity and compact.
Description
Technical field
The invention belongs to rare-earth boride material technology field, be specifically related to a kind of high purity high dense multicomponent rare earth boride (Ce
xBa
1-x) B
6Polycrystalline bulk material and preparation method thereof.
Background technology
Rare-earth boride is because its unique electronic structure has a lot of good physics, chemical properties.After J.M.Lafferty found that lanthanum hexaborane has excellent electron emission characteristic, the focus of research had mainly concentrated on LaB
6Be on master's the binary rare-earth boride, the research of multicomponent rare earth boride and use considerably less, therefore, be necessary different system multicomponent rare earth borides are strengthened research, study their performance such as preparation technology, constitutional features, physicochemical property and light, electricity, magnetic, heat, mechanics, be beneficial to further explore and enlarge new Application Areas.The traditional preparation process method of multicomponent rare earth boride generally was divided into for two steps: the first step adopts earlier methods such as fused salt electrolysis, magnesium heat, boron heat, norbide reduction to prepare the multicomponent rare earth boride powder, with powder through the chemical process removal of impurities purify, washing, dry, broken, screening; Second step adopted pressing methods again under high temperature (1800 ℃～2100 ℃) condition, and long-time (2～10h) sintering are prepared into the multicomponent rare earth boride block.The shortcoming of these methods is that sintering temperature is too high, and sintering time is oversize, and product is not fine and close, reaction not exclusively, product is impure, 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 purity high dense multicomponent rare earth boride (Ce is provided
xBa
1-x) B
6And 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 purity high dense multicomponent rare earth boride provided by the present invention consist of (Ce
xBa
1-x) B
6, wherein, 0.2≤x≤0.8.
The present invention adopts the direct current arc evaporative condenser to prepare multicomponent rare earth boride (Ce with the method that discharge plasma sintering (SPS) combines
xBa
1-x) B
6, concrete steps are as follows:
1) adopt the direct current arc evaporation condensing plant, earlier equipment is evacuated to 20Pa, applying argon gas cleans, and is evacuated to 2.5 * 10 again
-2Pa, collecting chamber applying argon gas afterwards, reaction chamber feeding volume ratio is 2～4: 1 hydrogen and argon gas, and total gas pressure is 0.07～0.9MPa, is anode with elemental metals Ce piece, metal W is a negative electrode, negative electrode and anode distance 2～4mm, reaction current 40～80A, response voltage is 25～60V, reaction times is 40～60min, preparation CeH
2Nanometer powder;
2) adopt the direct current arc evaporation condensing plant, earlier equipment is evacuated to 20Pa, applying argon gas cleans, and is evacuated to 2.5 * 10 again
-2Pa, collecting chamber applying argon gas afterwards, reaction chamber feeding volume ratio is 2～4: 1 hydrogen and argon gas, and total gas pressure is 0.07～0.9MPa, is anode with elemental metals Ba piece, metal W is a negative electrode, negative electrode and anode distance 2～4mm, reaction current 40～80A, response voltage is 25～40V, reaction times is 40～60min, preparation BaH
2Nanometer powder;
3) with CeH
2Nanometer powder, BaH
2In nanometer powder and the argon gas atmosphere of B powder below oxygen level is lower than 20ppm, press atomic ratio x: (1-x): 6 batchings, wherein pack into behind the grinding mixing in the graphite jig in 0.2≤x≤0.8, adds the axle pressure compression moulding of 10MPa in advance;
4) mould is placed the SPS sintering cavity, be lower than under the vacuum condition that argon gas atmosphere below the 20ppm or vacuum tightness is better than 10Pa in oxygen level, with the temperature rise rate intensification sintering of 120～160 ℃/min after 4 minutes, be forced into 30～60MPa again, sintering temperature is 1400～1600 ℃, insulation 5～15min cools to room temperature with the furnace, obtains multicomponent rare earth boride (Ce
xBa
1-x) B
6, principle is as shown in equation (1), (2) and (3).
xCeH
2(s)→xCe(s)+xH
2(g) (1)
(1-x)BaH
2(s)→(1-x)Ba(s)+(1-x)H
2(g) (2)
XCe (1)+(1-x) Ba (1)+6B (s) → Ce
xBa (
1-x) B
6(s) (3) wherein, the described CeH of step 1)
2The particle diameter of nanometer powder is 20～40nm; Step 2) described BaH
2The particle diameter of nanometer powder is 20～50nm; The particle diameter of the described B powder of step 3) is 20～40nm or 1～40 μ m.
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 (Ce
xBa
1-x) B
6Block materials density height, relative density can reach 99.56%, and Vickers' hardness reaches 2613Kg/mm
2, be the hexaboride pure phase through X-ray diffraction analysis, X-ray fluorescence spectra detects chemical purity and reaches 99.91%.
Description of drawings
(the Ce of Fig. 1, embodiment 1 preparation
0.2Ba
0.8) B
6The X-ray spectrogram of sintering block sample.
(the Ce of Fig. 2, embodiment 2 preparations
0.5Ba
0.5) B
6The X-ray spectrogram of sintering block sample.
(the Ce of Fig. 3, embodiment 3 preparations
0.8Ba
0.2) B
6The X-ray spectrogram of sintering block sample.
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) adopt the direct current arc using vaporization condensation process, equipment is evacuated to 20Pa earlier, and applying argon gas cleans, and is evacuated to 2.5 * 10 again
-2It is 2: 1 hydrogen and argon gas that Pa, collecting chamber applying argon gas afterwards, reaction chamber feed volume ratio, and total gas pressure is 0.9MPa, with elemental metals Ce piece is anode, and metal W is a negative electrode, negative electrode and anode distance 2～4mm, reaction current 80A, response voltage is 25V, and the reaction times is 40min, preparation CeH
2Nanometer powder;
2) adopt the direct current arc using vaporization condensation process, equipment is evacuated to 20Pa earlier, and applying argon gas cleans, and is evacuated to 2.5 * 10 again
-2It is 2: 1 hydrogen and argon gas that Pa, collecting chamber applying argon gas afterwards, reaction chamber feed volume ratio, and total gas pressure is 0.9MPa, with elemental metals Ba piece is anode, and metal W is a negative electrode, negative electrode and anode distance 2～4mm, reaction current 80A, response voltage is 25V, and the reaction times is 40min, preparation BaH
2Nanometer powder;
3) with CeH
2Nanometer powder, BaH
2Nanometer powder and B nanometer powder are in the argon gas atmosphere of 20ppm in oxygen level, press 0.2: 0.8: 6 batching of atomic ratio, pack into behind the grinding mixing in the graphite jig, add the axle pressure compression moulding of 10MPa in advance;
4) mould being placed the SPS sintering cavity, is in the argon gas atmosphere of 20ppm in oxygen level, after 4 minutes, is forced into 30MPa with the temperature rise rate intensification sintering of 120 ℃/min again, and sintering temperature is 1400 ℃, and insulation 15min cools to room temperature with the furnace, can obtain (Ce
0.2Ba
0.8) B
6The polycrystalline bulk material.
(the Ce of preparation
0.2Ba
0.8) B
6The block color is blue, XRD spectra as shown in Figure 1, as seen from the figure, the sample principal phase is BaB
6, no dephasign.Through the X-ray fluorescence spectra test shows, should (Ce
0.2Ba
0.8) B
6The chemical purity of sintering block reaches 99.91%.The relative density that records sample is 98.85%, and Vickers' hardness reaches 2320Kg/mm
2
Embodiment 2
1) adopt the direct current arc using vaporization condensation process, equipment is evacuated to 20Pa earlier, and applying argon gas cleans, and is evacuated to 2.5 * 10 again
-2It is 3: 1 hydrogen and argon gas that Pa, collecting chamber applying argon gas afterwards, reaction chamber feed volume ratio, and total gas pressure is 0.08MPa, with elemental metals Ce piece is anode, and metal W is a negative electrode, negative electrode and anode distance 2～4mm, reaction current 60A, response voltage is 30V, and the reaction times is 50min, preparation CeH
2Nanometer powder;
2) adopt the direct current arc using vaporization condensation process, equipment is evacuated to 20Pa earlier, and applying argon gas cleans, and is evacuated to 2.5 * 10 again
-2It is 3: 1 hydrogen and argon gas that Pa, collecting chamber applying argon gas afterwards, reaction chamber feed volume ratio, and total gas pressure is 0.08MPa, with elemental metals Ba piece is anode, and metal W is a negative electrode, negative electrode and anode distance 2～4mm, reaction current 60A, response voltage is 30V, and the reaction times is 50min, preparation BaH
2Nanometer powder;
3) with CeH
2Nanometer powder, BaH
2Nanometer powder and B nanometer powder are in the argon gas atmosphere of 10ppm in oxygen level, press 0.5: 0.5: 6 batching of atomic ratio, pack into behind the grinding mixing in the graphite jig, add the axle pressure compression moulding of 10MPa in advance;
4) mould being placed the SPS sintering cavity, is in the argon gas atmosphere of 10ppm in oxygen level, after 4 minutes, is forced into 50MPa with the temperature rise rate intensification sintering of 150 ℃/min again, and sintering temperature is 1500 ℃, and insulation 10min cools to room temperature with the furnace, can obtain (Ce
0.5Ba
0.5) B
6The polycrystalline bulk material.
(the Ce of preparation
0.5Ba
0.5) B
6The block color is blue, XRD spectra as shown in Figure 2, as seen from the figure, sample is CeB
6And BaB
6Two-phase, no dephasign.Through the X-ray fluorescence spectra test shows, should (Ce
0.5Ba
0.5) B
6The chemical purity of sintering block reaches 99.91%.The relative density that records sample is 99.56%, and Vickers' hardness reaches 2613Kg/mm
2
Embodiment 3
1) adopt the direct current arc using vaporization condensation process, equipment is evacuated to 20Pa earlier, and applying argon gas cleans, and is evacuated to 2.5 * 10 again
-2It is 4: 1 hydrogen and argon gas that Pa, collecting chamber applying argon gas afterwards, reaction chamber feed volume ratio, and total gas pressure is 0.07MPa, with elemental metals Ce piece is anode, and metal W is a negative electrode, negative electrode and anode distance 2～4mm, reaction current 40A, response voltage is 60V, and the reaction times is 60min, preparation CeH
2Nanometer powder;
2) adopt the direct current arc using vaporization condensation process, equipment is evacuated to 20Pa earlier, and applying argon gas cleans, and is evacuated to 2.5 * 10 again
-2It is 4: 1 hydrogen and argon gas that Pa, collecting chamber applying argon gas afterwards, reaction chamber feed volume ratio, and total gas pressure is 0.08MPa, with elemental metals Ba piece is anode, and metal W is a negative electrode, negative electrode and anode distance 2～4mm, reaction current 40A, response voltage is 60V, and the reaction times is 60min, preparation BaH
2Nanometer powder;
3) with CeH
2Nanometer powder, BaH
2Nanometer powder and B micron powder are in the argon gas atmosphere of 15ppm in oxygen level, press 0.8: 0.2: 6 batching of atomic ratio, pack into behind the grinding mixing in the graphite jig, add the axle pressure compression moulding of 10MPa in advance;
4) mould is placed the SPS sintering cavity, under the vacuum condition of 10Pa, after 4 minutes, be forced into 60MPa with the temperature rise rate intensification sintering of 160 ℃/min again, sintering temperature is 1600 ℃, and insulation 5min cools to room temperature with the furnace, can obtain (Ce
0.8Ba
0.2) B
6The polycrystalline bulk material.
(the Ce of preparation
0.8Ba
0.2) B
6The block color is blue, XRD spectra as shown in Figure 3, as seen from the figure, the sample principal phase is CeB
6, no dephasign.Through the X-ray fluorescence spectra test shows, should (Ce
0.8Ba
0.2) B
6The chemical purity of sintering block reaches 99.91%.The relative density that records sample is 99.11%, and Vickers' hardness reaches 2308Kg/mm
2
Claims (4)
1. multicomponent rare earth boride (Ce
xBa
1-x) B
6The preparation method, 0.2≤x≤0.8 is characterized in that, may further comprise the steps:
1) adopt the direct current arc evaporation condensing plant, earlier equipment is evacuated to 20Pa, applying argon gas cleans, and is evacuated to 2.5 * 10 again
-2Pa, collecting chamber applying argon gas afterwards, reaction chamber feeding volume ratio is 2～4: 1 hydrogen and argon gas, and total gas pressure is 0.07～0.1MPa, is anode with elemental metals Ce piece, metal W is a negative electrode, negative electrode and anode distance 2～4mm, reaction current 40～80A, response voltage is 25～60V, reaction times is 40～60min, preparation CeH
2Nanometer powder;
2) adopt the direct current arc evaporation condensing plant, earlier equipment is evacuated to 20Pa, applying argon gas cleans, and is evacuated to 2.5 * 10 again
-2Pa, collecting chamber applying argon gas afterwards, reaction chamber feeding volume ratio is 2～4: 1 hydrogen and argon gas, and total gas pressure is 0.07～0.9MPa, is anode with elemental metals Ba piece, metal W is a negative electrode, negative electrode and anode distance 2～4mm, reaction current 40～80A, response voltage is 25～40V, reaction times is 40～60min, preparation BaH
2Nanometer powder;
3) with CeH
2Nanometer powder, BaH
2In nanometer powder and the argon gas atmosphere of B powder below oxygen level is lower than 20ppm, press atomic ratio x: (1-x): 6 batchings, wherein pack into behind the grinding mixing in the graphite jig in 0.2≤x≤0.8, adds the axle pressure compression moulding of 10MPa in advance;
4) mould is placed the SPS sintering cavity, be lower than under the vacuum condition that argon gas atmosphere below the 20ppm or vacuum tightness is better than 10Pa in oxygen level, with the temperature rise rate intensification sintering of 120～160 ℃/min after 4 minutes, be forced into 30～60MPa again, sintering temperature is 1400～1600 ℃, insulation 5～15min cools to room temperature with the furnace, obtains multicomponent rare earth boride (Ce
xBa
1-x) B
6
2. method according to claim 1 is characterized in that, described CeH
2The particle diameter of nanometer powder is 20～40nm.
3. method according to claim 1 is characterized in that, described BaH
2The particle diameter of nanometer powder is 20～50nm.
4. method according to claim 1 is characterized in that, the particle diameter of described B powder is 20～40nm or 1～40 μ m.
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| CN102808215A (en) * | 2012-06-28 | 2012-12-05 | 北京工业大学 | Preparation method of large-dimension multi-element rare earth boride (Ce0.9Pr0.1)B6 single crystal |
| RU2540277C1 (en) * | 2013-09-27 | 2015-02-10 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования Кабардино-Балкарский государственный университет им. Х.М. Бербекова (КГБУ) | Electrolytic method of obtaining nanosized cerium hexaboride powder |
| CN107342201A (en) * | 2017-07-20 | 2017-11-10 | 信阳师范学院 | A kind of CeB6The preparation method of flexible Field Emission cathode material |
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