CN113184870A - Macro-particle-size-controllable LaB6Method for preparing powder - Google Patents
Macro-particle-size-controllable LaB6Method for preparing powder Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 19
- 238000005406 washing Methods 0.000 claims abstract description 18
- 239000007789 gas Substances 0.000 claims abstract description 17
- 229910025794 LaB6 Inorganic materials 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 230000001681 protective effect Effects 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000011049 filling Methods 0.000 claims abstract description 8
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 6
- 239000012153 distilled water Substances 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000002844 melting Methods 0.000 claims abstract description 5
- 230000008018 melting Effects 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000003825 pressing Methods 0.000 claims abstract description 5
- 238000000746 purification Methods 0.000 claims abstract description 5
- 238000001291 vacuum drying Methods 0.000 claims abstract description 5
- 238000005303 weighing Methods 0.000 claims abstract description 5
- 239000002253 acid Substances 0.000 claims abstract description 4
- 239000011261 inert gas Substances 0.000 claims abstract description 4
- 239000000047 product Substances 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 14
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M potassium chloride Inorganic materials [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 11
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000001103 potassium chloride Substances 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 8
- 238000000498 ball milling Methods 0.000 claims description 7
- 229910002249 LaCl3 Inorganic materials 0.000 claims description 6
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 6
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 claims description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 6
- 238000005554 pickling Methods 0.000 claims description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L magnesium chloride Substances [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 3
- 150000003841 chloride salts Chemical class 0.000 claims description 2
- 239000003701 inert diluent Substances 0.000 claims description 2
- -1 inert diluents Chemical class 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 239000003085 diluting agent Substances 0.000 description 7
- 238000009826 distribution Methods 0.000 description 6
- 229910052746 lanthanum Inorganic materials 0.000 description 6
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 5
- 239000011858 nanopowder Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229910052580 B4C Inorganic materials 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 229910015844 BCl3 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005049 combustion synthesis Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B35/00—Boron; Compounds thereof
- C01B35/02—Boron; Borides
- C01B35/04—Metal borides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Abstract
Macro-particle-size-controllable LaB6The preparation method of the powder comprises the following steps: weighing reaction materials in proportion to prepare an initial mixture; step (2) placing the initial mixture obtained in the step (1) in a planetary ball mill, uniformly mixing, and pressing on a hydraulic machine to obtain a blank body with the diameter of 80 mm multiplied by (35-45) mm; putting the medium blank body into a high-pressure reaction kettle, putting a detonator on the blank body, filling inert gas, washing the gas and exhausting the gas, then filling inert protective gas again for pressure maintaining, continuously heating to the melting point of the detonator, and carrying out self-propagating high-temperature synthesis reaction on the system to obtain a purple blocky initial product; step (4) crushing the initial product in the step (2) to obtain a powdery product, and performing acid washing and water washing treatment by adopting a hydrochloric acid solution and distilled water respectively to reach the purification standardThen placing the mixture in a vacuum drying oven for drying to obtain LaB6And (3) powder.
Description
Technical Field
The invention relates to a preparation technology of lanthanum hexaboride ultrafine powder.
Background
LaB6Lanthanum hexaboride is considered to be a material with great application value, is an excellent thermionic emitter, and has high melting point (2715 ℃), high brightness, low volatility, high mechanical strength, high Young modulus, high thermal conductivity, high electrical conductivity, high chemical stability, high neutron absorption capacity, strong radiation resistance, and good wear resistance and corrosion resistance. The difficulty existing at present is that the obtained product has larger particle size, is difficult to regulate and control, has lower purity and is difficult to realize industrial production, thereby influencing the application and the electron emission performance of the lanthanum hexaboride material, and because the polycrystalline block LaB6The electron emission performance of the composite is directly related to the granularity and the purity (especially the content of carbon impurities) of the powder, so that in order to obtain an industrial cathode material with good emission performance, a simple process route which has low energy consumption and is suitable for batch production is needed to prepare and synthesize LaB with high activity, high purity, ultrafine crystal grains and uniform grain size distribution6The polycrystalline powder material can be used for accelerating the application and improving the application value.
LaB6The synthesis method comprises the following steps: mechanochemical synthesis, elemental synthesis, aluminum flux, float zone, magnesium thermal, carbonThermal/boron carbide reduction methods, borothermal, Chemical Vapor Deposition (CVD), combustion synthesis methods, solid phase reaction methods, and the like. Review the present study with LaCl3、BCl3、H2Adopts CVD method to prepare LaB with diameter of 50 nm and length of several micrometers at 1000 deg.C6Nano-wire and has good emission performance. By boron carbide reduction/carbothermic, borothermic use of La2O3、B2O3Or B, C reaction system and La2O3-B、La2O3-B4C, obtaining powder with the average grain diameter of 6 mu m by the reaction system. With LaCl3、NaBH4Taking molten KCl/LiCl salt as a reaction medium in a vacuum state, and adopting different reaction temperatures and stoichiometric ratios to obtain cubic/spherical nano LaB with good crystallinity6The grain diameter is between 20 nm and 100 nm. With La2O3、B2O3Mg and I2Is prepared by heating raw materials to 90 ℃ at a heating rate of 2 DEG/min in an Ar atmosphere in a quartz tube to synthesize the high-purity product with the particle diameter of 61.3 +/-2.0 nm, the lattice constant of 4.153A and the specific surface area of 1.3 m2Lam/g6And (4) nanocrystals. From recent research work, although micron-sized and nano-sized LaB is obtained6The powder is prepared in a trace manner, and is not suitable for large-scale production.
Disclosure of Invention
The invention aims to provide a macro-granularity controllable LaB6A method for preparing powder.
The invention relates to a macro-granularity controllable LaB6The preparation method of the powder comprises the following steps:
weighing reaction materials in proportion to prepare an initial mixture;
step (2) placing the initial mixture obtained in the step (1) in a planetary ball mill, uniformly mixing, and pressing on a hydraulic machine to obtain a blank body with the diameter of 80 mm multiplied by (35-45) mm;
putting the medium blank body into a high-pressure reaction kettle, putting a detonator on the blank body, filling inert gas, washing the gas and exhausting the gas, then filling inert protective gas again for pressure maintaining, continuously heating to the melting point of the detonator, and carrying out self-propagating high-temperature synthesis reaction on the system to obtain a purple blocky initial product;
step (4) crushing the initial product obtained in the step (2) to obtain a powdery product, respectively carrying out acid washing and water washing treatment by adopting a hydrochloric acid solution and distilled water, and placing the powdery product in a vacuum drying oven for drying after reaching the purification standard to obtain LaB6And (3) powder.
The invention has the advantages that: the energy consumption is low, the cost is low, once ignition is carried out, extra energy is not needed, and the reaction can be carried out when the heating temperature reaches 270-300 ℃; the process is simple and the operation is simple; short production period and high efficiency, and can prepare kilogram-grade superfine high-purity LaB at one time6Powder and uniform particle size distribution. The average particle size of the product is regulated and controlled by changing the content of the diluent to be reduced from 1.5-4 mu m to below 0.5 mu m; or changing the lanthanum source to obtain the product nano powder with the grain diameter of less than 80 nm.
Drawings
FIG. 1 shows LaB prepared by the present invention6XRD pattern of powder, FIG. 2 is LaB prepared by the invention6(15 wt.% KCl) SEM image of the powder, FIG. 3 is a drawing of the LaB prepared by the present invention6(45 wt.% KCl) SEM image of the powder, FIG. 4 is a drawing of the LaB prepared by the present invention6Particle size distribution of powder (0 wt.% diluent), FIG. 5 is a graph of LaB prepared according to the present invention6Particle size distribution of (15 wt.% KCl) powder, FIG. 6 is a graph of LaB prepared by the present invention6(45 wt.% KCl) particle size distribution diagram of the powder, FIG. 7 is a diagram of the LaB preparation according to the invention6XRD pattern of nano powder, FIG. 8 is LaB prepared by the invention6TEM image of nanopowder.
Detailed Description
The invention relates to a macro-granularity controllable LaB6The preparation method of the powder comprises the following steps:
weighing reaction materials in proportion to prepare an initial mixture;
step (2) placing the initial mixture obtained in the step (1) in a planetary ball mill, uniformly mixing, and pressing on a hydraulic machine to obtain a blank body with the diameter of 80 mm multiplied by (35-45) mm;
putting the medium blank body into a high-pressure reaction kettle, putting a detonator on the blank body, filling inert gas, washing the gas and exhausting the gas, then filling inert protective gas again for pressure maintaining, continuously heating to the melting point of the detonator, and carrying out self-propagating high-temperature synthesis reaction on the system to obtain a purple blocky initial product;
step (4) crushing the initial product obtained in the step (2) to obtain a powdery product, respectively carrying out acid washing and water washing treatment by adopting a hydrochloric acid solution and distilled water, and placing the powdery product in a vacuum drying oven for drying after reaching the purification standard to obtain LaB6And (3) powder.
According to the preparation method, the reaction materials in the step (1) and the mass ratio of the reaction materials are La2O3：B2O3: mg = 4.9: 29: 103, chloride salts, i.e. inert diluents, such as KCl, NaCl, MgCl2One of the two is adopted, and the adding amount of the one is 0-45 wt% of the total mass of the reaction materials; LaCl3•7H2O：B2O3：Mg = 4.9：14.7：85.8。
According to the preparation method, the ball milling parameters in the step (2) are that the time is 8-16 h, the rotating speed is 150 r/min, and the ball-to-material ratio is 2: 1; the uniaxial pressure of the press is 30-50 MPa.
According to the preparation method, the preheating temperature in the step (3) is 270-300 ℃; the protective atmosphere is argon, the gas washing pressure is 0.5 MPa, and the pressure maintaining pressure is 2-4 MPa.
According to the preparation method, the hydrochloric acid solution in the step (4) is 4 mol/L hydrochloric acid solution, and the excess is 50 vol.%; during the pickling process, carrying out multiple pH test paper tests on the pickling solution until the color of the test paper is unchanged; in the water washing process, a silver nitrate solution is adopted, so that no precipitate is generated; then dried under vacuum at 100 ℃ for 24 h.
According to the above preparation method, LaB6The particle size of the powder is reduced from 1.5-4 μm to below 1 μm, and the minimum average particle size is 345 nm.
The following are specific examples of the present invention, and the technical solutions of the present invention will be further described with reference to the examples, but the present invention is not limited to the examples.
Example 1:
the reactant feedstock in this example was La2O3（≥99.99%）、B2O3（>98%）、Mg（>99.8%, 325 mesh), experimental conditions: the ball milling time is 8h, the pressurizing pressure is 40 MPa, the protective atmosphere pressure is 2 MPa, KCl is selected as a diluent, the adding amount is 0 wt.%, the ball milling time is 8h, the pressurizing pressure is 40 MPa, the protective atmosphere pressure is 2 MPa, and the method specifically comprises the following steps:
(1) lanthanum oxide, boron oxide and magnesium powder are used as raw materials, and the mass ratio of the three raw materials is La2O3：B2O3: mg = 4.9: 29: 103, weighing the materials by using an analytical balance, wherein the initial mixture is 2 kg;
(2) placing the initial mixture in a QM-ISP4 planetary gear ball mill at a ball-material ratio of 2:1 and a rotating speed of 150 r/min for mixing for 8 hours to obtain a mixed material which is uniformly mixed and fully contacts with each reactant;
(3) pressing the uniformly mixed materials into a plurality of blanks with phi of 80 mm multiplied by 45 mm by adopting a QYL50 type hydraulic press under the condition that the uniaxial pressure is 40 MPa;
(4) and placing the blank in a Cu crucible, placing a plurality of flaky ignition agents on the surface of the blank, then placing the Cu crucible in a reaction container, closing a bin gate, and screwing screws to ensure the tightness. And finally, injecting argon gas of 0.5 MPa into the container, standing for 5 min, and discharging the gas. And then, opening a heating switch, heating to 180 ℃, opening an air valve to exhaust gas, injecting 2 MPa argon into the container again, and continuing heating. When the temperature reaches about 290 ℃, the reaction is generated, the air pressure is rapidly increased from 2 MPa to 4 or 5 MPa, the temperature is rapidly increased by dozens of degrees or even hundreds of degrees, the reaction is completed within a few minutes, and then the heating switch is closed. Taking out the sample when the container is cooled to room temperature to obtain a purple block;
(5) crushing the obtained block by a crusher to obtain a powdery combustion product;
(6) adding powdery combustion product into 12 mol/L hydrochloric acid, diluting to 4 mol/L hydrochloric acid, acid-washing, stirring with glass rod, cooling to room temperaturePutting the mixture into a heat collection type magnetic stirrer for stirring for 30 min to ensure that HCl and MgO react more fully, and measuring the pH value by adopting a pH meter or pH test paper; if the pH paper or the pH meter shows a pH value of 4 or less, the reaction is completely acidic. Standing for 24h for powder sedimentation, pouring the pickling solution into a beaker, washing the settled powder in the beaker with distilled water to remove the foreign matter MgCl2Stirring in a heat-collecting constant-temperature magnetic stirrer for 30 min, titrating with silver nitrate solution, standing for 8h without precipitate, sequentially and circularly until the precipitation reaches the purification standard, standing for 24h, and drying in a vacuum drying oven for 24h to obtain pure LaB6And (3) ultrafine powder.
Example 2:
in the embodiment, KCl is used as a diluent, the addition amount is 15 wt.%, the ball milling time is 8h, the pressure of a green compact is 40 MPa, and the pressure of a protective atmosphere is 2 MPa, and the specific steps are the same as those in embodiment 1.
Example 3:
in the embodiment, KCl is selected as a diluent, the addition amount is 45 wt.%, the ball milling time is 8h, the pressure of a green compact is 40 MPa, and the pressure of a protective atmosphere is 2 MPa, and the specific steps are the same as those in embodiment 1.
Example 4:
LaCl is selected for use in this embodiment3•7H2O instead of La2O3As lanthanum source, LaCl3•7H2O、B2O3And Mg serving as raw materials, wherein the mass ratio is LaCl3•7H2O：B2O3: mg = 4.9: 14.7: 85.8, the ball milling time is 12 h, the pressure of the green compact is 30 MPa, and the pressure of the protective atmosphere is 2 MPa, and the specific steps are the same as those in example 1.
As shown in FIG. 1, the sample prepared by the present invention is LaB6Phase, as shown in FIG. 2 and FIG. 3, LaB prepared by the present invention6SEM image of the powder, in which LaB can be seen with increasing diluent content6The particle size distribution is uniform, gradually decreases and is cubic. As shown in FIGS. 4 and 5, LaB can be controlled by changing the content of the diluent6The average particle size of the powder is reduced from 1.5-4 μm to 0.3 μm. As shown in fig. 6LaB prepared by changing lanthanum source6TEM image of nano powder, LaB is calculated by Sherle formula6The particle size of the powder is reduced from 2.5 μm to below 80 nm.
Claims (6)
1. Macro-particle-size-controllable LaB6The preparation method of the powder is characterized by comprising the following steps:
weighing reaction materials in proportion to prepare an initial mixture;
step (2) placing the initial mixture obtained in the step (1) in a planetary ball mill, uniformly mixing, and pressing on a hydraulic machine to obtain a blank body with the diameter of 80 mm multiplied by (35-45) mm;
putting the medium blank body into a high-pressure reaction kettle, putting a detonator on the blank body, filling inert gas, washing the gas and exhausting the gas, then filling inert protective gas again for pressure maintaining, continuously heating to the melting point of the detonator, and carrying out self-propagating high-temperature synthesis reaction on the system to obtain a purple blocky initial product;
step (4) crushing the initial product obtained in the step (2) to obtain a powdery product, respectively carrying out acid washing and water washing treatment by adopting a hydrochloric acid solution and distilled water, and placing the powdery product in a vacuum drying oven for drying after reaching the purification standard to obtain LaB6And (3) powder.
2. The macro-granularity controllable LaB as claimed in claim 16The preparation method of the powder is characterized in that the reaction materials in the step (1) and the mass ratio of the reaction materials are La2O3：B2O3: mg = 4.9: 29: 103, chloride salts, i.e. inert diluents, such as KCl, NaCl, MgCl2One of the two is adopted, and the adding amount of the one is 0-45 wt% of the total mass of the reaction materials; LaCl3•7H2O：B2O3：Mg = 4.9：14.7：85.8。
3. The macro-granularity controllable LaB as claimed in claim 16The preparation method of the powder is characterized in that the ball milling parameters in the step (2) are that the time is 8-16 h, the rotating speed is 150 r/min, and the ball material isThe ratio is 2: 1; the uniaxial pressure of the press is 30-50 MPa.
4. The macro-granularity controllable LaB as claimed in claim 16The preparation method of the powder is characterized in that the preheating temperature in the step (3) is 270-300 ℃; the protective atmosphere is argon, the gas washing pressure is 0.5 MPa, and the pressure maintaining pressure is 2-4 MPa.
5. The macro-granularity controllable LaB as claimed in claim 16The preparation method of the powder is characterized in that the hydrochloric acid solution in the step (4) is 4 mol/L hydrochloric acid solution, and the excessive amount is 50 vol.%; during the pickling process, carrying out multiple pH test paper tests on the pickling solution until the color of the test paper is unchanged; in the water washing process, a silver nitrate solution is adopted, so that no precipitate is generated; then dried under vacuum at 100 ℃ for 24 h.
6. The macro-granularity controllable LaB as claimed in claim 16The preparation method of the powder is characterized in that the LaB6The particle size of the powder is reduced from 1.5-4 μm to below 1 μm, and the minimum average particle size is 345 nm.
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| CN114933310A (en) * | 2022-06-02 | 2022-08-23 | 安阳工学院 | Preparation method of nano hexaboride powder |
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