CN112207287B - Preparation method and application of yttrium oxide nanoparticle-doped nano molybdenum powder - Google Patents
Preparation method and application of yttrium oxide nanoparticle-doped nano molybdenum powder Download PDFInfo
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- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 111
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 150000003746 yttrium Chemical class 0.000 claims abstract description 103
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims abstract description 93
- 239000002245 particle Substances 0.000 claims abstract description 72
- 239000011852 carbon nanoparticle Substances 0.000 claims abstract description 58
- 239000002105 nanoparticle Substances 0.000 claims abstract description 58
- 239000000843 powder Substances 0.000 claims abstract description 43
- 239000002131 composite material Substances 0.000 claims abstract description 42
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000007788 liquid Substances 0.000 claims abstract description 35
- 239000000203 mixture Substances 0.000 claims abstract description 35
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 29
- 239000001257 hydrogen Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 27
- 230000009467 reduction Effects 0.000 claims abstract description 27
- 238000001704 evaporation Methods 0.000 claims abstract description 11
- 238000005507 spraying Methods 0.000 claims abstract description 11
- 229910001182 Mo alloy Inorganic materials 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 10
- 229910001175 oxide dispersion-strengthened alloy Inorganic materials 0.000 claims abstract description 6
- 238000005245 sintering Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 31
- 239000004094 surface-active agent Substances 0.000 claims description 29
- 239000000463 material Substances 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 19
- 238000000889 atomisation Methods 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 239000012266 salt solution Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 239000011833 salt mixture Substances 0.000 claims 1
- 238000010899 nucleation Methods 0.000 abstract description 9
- 230000006911 nucleation Effects 0.000 abstract description 7
- 239000002086 nanomaterial Substances 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000004321 preservation Methods 0.000 abstract description 4
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 19
- 229910052750 molybdenum Inorganic materials 0.000 description 18
- 239000011733 molybdenum Substances 0.000 description 18
- 238000002156 mixing Methods 0.000 description 14
- 229920001223 polyethylene glycol Polymers 0.000 description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 description 10
- 230000008569 process Effects 0.000 description 6
- 239000002667 nucleating agent Substances 0.000 description 5
- 238000011946 reduction process Methods 0.000 description 5
- 239000000956 alloy Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000002490 spark plasma sintering Methods 0.000 description 3
- 229910000347 yttrium sulfate Inorganic materials 0.000 description 3
- RTAYJOCWVUTQHB-UHFFFAOYSA-H yttrium(3+);trisulfate Chemical compound [Y+3].[Y+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RTAYJOCWVUTQHB-UHFFFAOYSA-H 0.000 description 3
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000007123 defense Effects 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 238000009766 low-temperature sintering Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 150000002603 lanthanum Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
- B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
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- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
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Abstract
The invention discloses a preparation method of nanometer molybdenum powder doped with yttrium oxide nanoparticles, which comprises the following steps: firstly, dispersing commercial micron-sized molybdenum trioxide and carbon nano-particles in a solution and evaporating to dryness to obtain composite powder; secondly, spraying the superfine/nano yttrium salt liquid drops into the composite powder, and drying to obtain a mixture containing yttrium salt; thirdly, the mixture containing yttrium salt is subjected to heat preservation and reduction in sections to obtain the ultrafine doped MoO2(ii) a Fourthly, doping the superfine MoO2Reducing with hydrogen to obtain nanometer molybdenum powder doped with yttrium oxide nanometer particles; the invention also provides application of the yttrium oxide nanoparticle-doped nano molybdenum powder in preparing a nano-structure oxide dispersion strengthened molybdenum alloy by sintering. According to the invention, the preparation of the composite powder is combined with two-step reduction, so that the nucleation number of the reduction product is increased, the granularity of the reduction product is refined, the regulation and control of the granularity of the doped yttrium oxide nano-particles and molybdenum powder are realized, and the raw material cost is reduced; the application method of the invention is simple and easy to realize.
Description
Technical Field
The invention belongs to the technical field of preparation of nano powder materials, and particularly relates to a preparation method and application of yttrium oxide nanoparticle-doped nano molybdenum powder.
Background
Most molybdenum products are indispensable key materials for national defense and national economy departments, and have important application in the fields of aerospace, military, chemistry, nuclear energy, metallurgy and the like. Although metal molybdenum materials have a series of excellent physical, chemical and mechanical properties, pure metal molybdenum has the defects of easy oxidation at high temperature, low recrystallization temperature, high plastic-brittle transition temperature, low-temperature brittleness, easy brittle fracture after recrystallization, high strength, toughness, hardness, wear resistance and the like, and the increasing requirements of civil and military industry and national defense fields on the superior comprehensive properties of the molybdenum materials are difficult to meet. These deficiencies limit the processing and application of molybdenum and its alloys. In order to improve various properties of molybdenum metal products and expand the application range of molybdenum and molybdenum alloy products, a great deal of research on the performance optimization of molybdenum and molybdenum alloy materials has been conducted by many researchers at home and abroad. Among them, the design and preparation of ultra-fine grain nano-structured dispersion-strengthened molybdenum alloy materials are considered to be important ways to obtain molybdenum-based materials with superior comprehensive properties. The rare earth oxide nano-particle doped molybdenum powder is considered to be a key raw material for preparing ultra-fine grain nano-structure molybdenum and alloy materials thereof by powder metallurgy due to the excellent characteristics of the rare earth oxide nano-particle doped molybdenum powder.
At present, methods for preparing yttrium oxide doped molybdenum powder are divided into three categories: mixing of a solid molybdenum source (e.g., molybdenum oxide) with a solid oxide powder (S-S mixing), mixing of a solid molybdenum source with an oxide precursor solution (e.g., nitrate solution) (S-L mixing), and mixing of a liquid phase molybdenum precursor (e.g., ammonium molybdate solution) with an oxide precursor solution (L-L mixing). In general, L-L mixing and S-L mixing ratios S-S have better mixing results. However, the conventional S-L and L-L doping processes dope oxide particles with a difficult particle size and uniformity, generally with a large particle size and poor uniformity, due to the difficulty in controlling nucleation, growth, and final particle size during the evaporation of the solution. In addition, how to simultaneously realize the control of the particle sizes of the molybdenum and yttrium oxide doped phases in the process of preparing the molybdenum powder by reducing the molybdenum oxide is always a great challenge. Therefore, the efficient and low-cost preparation of nano-molybdenum powder doped with yttrium oxide nanoparticles remains a great problem.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide a method for preparing nanometer molybdenum powder doped with yttrium oxide nanoparticles, aiming at the defects of the prior art. According to the invention, superfine/nano yttrium salt is dripped into the composite powder formed by dispersing the carbon nano-particles and the micron-sized molybdenum trioxide, the mixing degree is improved, then two-step reduction is carried out in sequence, the carbon nano-particles and the yttrium salt nano-particles are respectively used as nucleating agents, the nucleation number of corresponding reduction products is increased, the granularity of the reduction products is refined, and meanwhile, the regulation and control of the granularity of the doped yttrium oxide nano-particles and molybdenum powder are realized, so that the nano-molybdenum powder doped with the yttrium oxide nano-particles is obtained.
In order to solve the technical problems, the invention adopts the technical scheme that: a preparation method of nanometer molybdenum powder doped with yttrium oxide nanoparticles is characterized by comprising the following steps:
step one, ultrasonically dispersing commercial micron-sized molybdenum trioxide and carbon nano-particles in an ethanol solution with the aid of a surfactant, and then stirring and evaporating to dryness to obtain composite powder;
step two, carrying out ultrasonic atomization on an yttrium salt solution to form ultrafine/nano yttrium salt liquid drops, then uniformly spraying the ultrafine/nano yttrium salt liquid drops into the composite powder obtained in the step one, and drying the ultrafine/nano yttrium salt liquid drops to obtain a mixture containing yttrium salt;
step three, respectively preserving the yttrium salt-containing mixture obtained in the step two for 2-4 h at the temperature of 520-540 ℃ and the temperature of 560-590 ℃ in sequence to obtain superfine doped MoO2；
Step four, the superfine doped MoO obtained in the step three is used2And (3) carrying out hydrogen reduction after laying to obtain the nano molybdenum powder doped with yttrium oxide nano particles.
Firstly, carbon nano-particles with excellent dispersibility and micron-sized molybdenum trioxide are ultrasonically dispersed in an ethanol solution under the assistance of a surfactant, so that the carbon nano-particles are coated on the surface of the molybdenum trioxide to form mixed powder, then superfine/nano yttrium salt liquid drops prepared by ultrasonic atomization are uniformly sprayed, and the mixed powder is dried to obtain doped ultra-fine/nano yttrium salt liquid dropsAn yttrium salt-containing mixture doped with yttrium salt nanoparticles; then carrying out two-stage heating and heat preservation reduction on the mixture containing yttrium salt, wherein in the reduction process, the carbon nano particles are used as a reducing agent to carry out MoO3Reduction to MoO2Meanwhile, the carbon nano-particles coated on the surface of the molybdenum trioxide provide a large number of nucleation points as a nucleating agent, so that MoO is greatly improved2Nucleation number of (1) and significant refinement of MoO2In addition, MoO during the reduction3The easy migration characteristic enables MoO2Mixing with doped phase yttrium salt nano-particles more uniformly to obtain superfine doped MoO2(ii) a Doping the superfine MoO2After laying, hydrogen is used as a reducing agent for hydrogen reduction, so that MoO2Reducing the yttrium salt to Mo, wherein in the reduction process, the doped phase yttrium salt nano particles are used as a nucleating agent, the nucleation number of molybdenum is increased, the granularity of molybdenum powder is further refined, meanwhile, the yttrium salt nano particles are converted in situ and maintain the granularity of the original yttrium salt nano particles to generate yttrium oxide nano particles, and meanwhile, the regulation and control of the granularity of the doped yttrium oxide nano particles and the molybdenum powder are realized, and the yttrium oxide nano particle doped molybdenum powder is obtained.
The preparation method of the yttrium oxide nanoparticle-doped nano molybdenum powder is characterized in that in the first step, the average particle size of the commercial micron-sized molybdenum trioxide is 1-5 mu m, and the mass purity is not less than 99.5%. The invention only needs to adopt the commercial micron-sized molybdenum trioxide with the performance as the raw material, does not need to adopt superfine/nano-sized molybdenum trioxide, effectively reduces the cost of the raw material, and is easy for engineering application.
The preparation method of the yttrium oxide nanoparticle-doped nano molybdenum powder is characterized in that in the step one, the average particle size of the carbon nanoparticles is 10-70 nm, the mass content of carbon in the carbon nanoparticles is more than 98%, and the adding mass of the carbon nanoparticles is 3.9-4.1% of that of commercial micron-sized molybdenum trioxide; the surfactant is one or more than two of PEG, PVP and PVA, and the adding mass of the surfactant is 0.2-1.2% of the total mass of the carbon nano particles and the commercial micron-sized molybdenum trioxide. The carbon nanoparticles with the preferred average particle size and carbon content have high specific surface area, excellent dispersibility and preferred combinationThe added mass is more easily and uniformly dispersed in MoO3Surface, improving the uniform mixing degree; the preferred surfactant and the added mass avoid the agglomeration of carbon nano particles, and further enhance the uniform mixing degree of the composite powder.
The preparation method of the yttrium oxide nanoparticle-doped nano molybdenum powder is characterized in that in the second step, the yttrium salt solution is yttrium soluble nitrate or sulfate, the concentration of the yttrium salt solution is 0.01-0.2 g/mL, and the mass of yttrium salt in the sprayed superfine/nano yttrium salt liquid drop is 0.05-3% of the mass of molybdenum element in the composite powder; the atomization vibration frequency is 0.2 MHz-2.5 MHz, and the average particle size of yttrium salt in the mixture containing yttrium salt is 10 nm-50 nm. The optimized type and concentration of the yttrium salt solution and the spraying quality of the yttrium salt liquid drops ensure that the yttrium salt is fully dispersed in the composite powder; the optimized atomization parameters ensure that yttrium salt doped in the yttrium salt-containing mixture is nanoparticles, so that the yttrium salt-containing mixture is beneficial to the subsequent in-situ generation of yttrium oxide nanoparticles through hydrogen reduction, and the in-situ particle size controllable generation of the yttrium oxide nanoparticles is realized.
The preparation method of the yttrium oxide nanoparticle-doped nano molybdenum powder is characterized in that the hydrogen reduction temperature in the fourth step is 750-900 ℃, and the heat preservation time is 1-3 h.
The preparation method of the yttrium oxide nanoparticle-doped nano molybdenum powder is characterized in that in the fourth step, a programmed heating method is adopted for hydrogen reduction, and the heating rate is 5-20 ℃/min; the mass purity of the hydrogen atmosphere is more than 99.9 percent, and the superfine doped MoO2The thickness of the laid material layer is 5 mm-25 mm. Preferably by controlling the hydrogen reduction process, the temperature rise rate and the ultrafine doping of MoO2The thickness of the material layer after being laid is enough to ensure that MoO is generated in the hydrogen reduction process2Generating MoO with proper concentration2(OH)2Thereby having certain migration capacity, being beneficial to the dispersion nucleation and growth of molybdenum particles, leading the molybdenum particles to have good dispersibility and further controlling the granularity of the molybdenum powder.
The preparation method of the yttrium oxide nanoparticle-doped nano molybdenum powder is characterized in that in the step four, the average particle size of the molybdenum powder is 60 nm-160 nm, and the average particle size of the yttrium oxide nanoparticle-doped nano molybdenum powder is 10 nm-50 nm. The optimized nanometer molybdenum powder doped with yttrium oxide nanometer particles is suitable for preparing nanometer structure oxide dispersion strengthening molybdenum alloy by low-temperature sintering.
In addition, the invention also provides application of the yttrium oxide nanoparticle-doped nano molybdenum powder prepared by the method, which is characterized in that the nano molybdenum powder doped with yttrium oxide nanoparticles is sintered to prepare the nano-structure oxide dispersion strengthened molybdenum alloy.
Compared with the prior art, the invention has the following advantages:
1. the invention sprays the ultra-fine/nano yttrium salt drops formed by ultrasonic atomization into the composite powder formed by dispersing the carbon nano-particles and the micron-sized molybdenum trioxide to obtain the yttrium salt-containing mixture doped with the yttrium salt nano-particles, improves the uniform mixing degree, then sequentially carries out two-step reduction, respectively uses the carbon nano-particles and the yttrium salt nano-particles as nucleating agents to improve the nucleation number of corresponding reduction products, refines the granularity of the reduction products, simultaneously realizes the regulation and control of the granularity of the doped yttrium oxide nano-particles and molybdenum powder, obtains the nano molybdenum powder doped with the yttrium oxide nano-particles, and reduces the cost of preparation raw materials.
2. The invention adopts carbon nano-particles with smaller particle size and excellent dispersibility as MoO3Reduction to MoO2Nucleating agent in the process obviously improves MoO2Nucleation number of (1), and refining MoO2The granularity of the particles is beneficial to obtaining the nanometer molybdenum powder doped with the yttrium oxide nanometer particles.
3. The invention adopts ultrasonic atomization to prepare superfine/nano yttrium salt liquid drops, and the superfine/nano yttrium salt liquid drops are sprayed into the composite powder and then dried to separate out a mixture containing yttrium salt, thereby realizing the doping of yttrium salt nano particles with low cost, high efficiency and controllable granularity, and further realizing the controllable generation of in-situ granularity of yttrium oxide nano particles.
4. According to the invention, the carbon nano-particles and commercial micron-sized molybdenum trioxide are mixed and dispersed firstly, and then ultra-fine/nano yttrium salt liquid drops are sprayed, so that uniform dispersion of yttrium salt nano-particles of a mixture containing yttrium salt is realized.
5. The invention controls MoO2Ultra-fine doped MoO in the process of reduction to Mo2The thickness of the laid material layer and the hydrogen reduction process parameters ensure that the molybdenum particles are fully dispersed, nucleated and grown, thereby being beneficial to obtaining the nano molybdenum powder doped with the yttrium oxide nano particles.
6. The preparation method is simple, high in efficiency, low in cost and easy for engineering application.
7. In the yttrium oxide nanoparticle-doped molybdenum powder prepared by the invention, the average particle size of the molybdenum powder is 60 nm-160 nm, and the average particle size of the yttrium oxide nanoparticle-doped molybdenum powder is 10 nm-50 nm, so that the yttrium oxide nanoparticle-doped molybdenum powder is suitable for preparing a nano-structure oxide dispersion strengthened molybdenum alloy by low-temperature sintering.
8. In the preparation method, the lanthanum salt solution can be used for replacing the yttrium salt solution to prepare the nano molybdenum powder doped with the lanthanum oxide nano particles, so that the preparation method has excellent popularization and application performance.
The technical solution of the present invention is further described in detail by the accompanying drawings and examples.
Drawings
Fig. 1 is an XRD pattern of nano molybdenum powder doped with yttria nanoparticles prepared in example 1 of the present invention.
Fig. 2 is an SEM image of nano molybdenum powder doped with yttrium oxide nanoparticles prepared in example 1 of the present invention.
Detailed Description
The preparation method of the yttrium oxide nanoparticle-doped nano molybdenum powder of the present invention is described in detail in examples 1 to 7.
Example 1
The embodiment comprises the following steps:
step one, ultrasonically dispersing commercial micron-sized molybdenum trioxide and carbon nano-particles in an ethanol solution under the assistance of a surfactant PVP, and then stirring and evaporating at 70 ℃ to dryness to obtain composite powder;
the commercial micron-sized molybdenum trioxide has an average particle size of 4.5 μm and a mass purity of 99.8%;
the average particle size of the carbon nano-particles is 20nm, the mass content of carbon in the carbon nano-particles is 99%, and the adding mass of the carbon nano-particles is 4.0% of the mass of commercial micron-sized molybdenum trioxide; the added mass of the surface active agent PVP is 0.3 percent of the total mass of the carbon nano particles and the commercial micron-sized molybdenum trioxide;
step two, ultrasonically atomizing 0.02g/mL yttrium nitrate solution into superfine/nano yttrium salt liquid drops by adopting an ultrasonic nano atomizer, then uniformly spraying the superfine/nano yttrium salt liquid drops into the composite powder obtained in the step one according to the proportion of adding 15mL yttrium nitrate solution into 100g of composite powder, and drying to obtain a mixture containing yttrium salt; the mass of yttrium salt in the sprayed superfine/nano yttrium salt liquid drop is 0.45 percent of the mass of molybdenum element in the composite powder; the atomization vibration frequency is 1.7MHz, and the average particle size of yttrium nitrate in the yttrium salt-containing mixture is 20 nm;
step three, sequentially preserving the yttrium salt-containing mixture obtained in the step two for 2 hours at 540 ℃ and 580 ℃ to obtain the superfine doped MoO2(ii) a The ultra-fine doped MoO2Has an average particle size of 190 nm;
step four, the superfine doped MoO obtained in the step three is used2Laying until the thickness of a material layer is 15mm, then placing the material layer in a hydrogen atmosphere with the mass purity of 99.99 percent, adopting a programmed heating method, heating to 850 ℃ at the speed of 10 ℃/min, and preserving heat for 2h to carry out hydrogen reduction to obtain nano molybdenum powder doped with yttrium oxide nano particles; in the yttrium oxide nanoparticle-doped molybdenum nano-powder, the average particle size of the molybdenum powder is 90nm, and the average particle size of the yttrium oxide nanoparticle-doped molybdenum powder is 20 nm.
Fig. 1 is an XRD pattern of the nano molybdenum powder doped with yttria nanoparticles prepared in this example, and as can be seen from fig. 1, the pattern only has a diffraction peak of molybdenum, but the particle size and content of yttria are both small and cannot be detected, which illustrates that the nano molybdenum powder prepared by the method of the present invention.
Fig. 2 is an SEM image of the nano molybdenum powder doped with yttrium oxide nanoparticles prepared in this example, and it can be seen from fig. 2 that the doped yttrium oxide nanoparticles prepared in this example have a small particle size and excellent dispersibility, wherein the average particle size of the yttrium oxide nanoparticles is 20 nm.
The surfactant in this example may also be one or more of PEG, PVP, and PVA in addition to PVP.
Example 2
The embodiment comprises the following steps:
step one, ultrasonically dispersing commercial micron-sized molybdenum trioxide and carbon nano-particles in an ethanol solution with the aid of a surfactant PEG-1000, and stirring and evaporating at 75 ℃ to dryness to obtain composite powder;
the commercial micron-sized molybdenum trioxide has an average particle size of 1.5 μm and a mass purity of 99.99%;
the average particle size of the carbon nano-particles is 10nm, the mass content of carbon in the carbon nano-particles is 99.5%, and the adding mass of the carbon nano-particles is 3.8% of the mass of commercial micron-sized molybdenum trioxide; the added mass of the surfactant PEG-1000 is 0.2 percent of the total mass of the carbon nano particles and the commercial micron-sized molybdenum trioxide;
step two, ultrasonically atomizing 0.01g/mL yttrium nitrate solution into superfine/nano yttrium salt liquid drops by adopting an ultrasonic nano atomizer, then uniformly spraying the superfine/nano yttrium salt liquid drops into the composite powder obtained in the step one according to the proportion of adding 15mL yttrium nitrate solution into 100g of composite powder, and drying to obtain a mixture containing yttrium salt; the mass of yttrium salt in the sprayed superfine/nano yttrium salt liquid drop is 0.225 percent of the mass of molybdenum element in the composite powder; the atomization vibration frequency is 2.4MHz, and the average particle size of yttrium nitrate in the yttrium salt-containing mixture is 10 nm;
step three, sequentially preserving the yttrium salt-containing mixture obtained in the step two for 2 hours at the conditions of 520 ℃ and 590 ℃ to obtain the superfine doped MoO2(ii) a The ultra-fine doped MoO2Has an average particle size of 120 nm;
step four, the superfine doped MoO obtained in the step three is used2Laying until the thickness of a material layer is 12mm, then placing the material layer in a hydrogen atmosphere with the mass purity of 99.999 percent, adopting a programmed heating method, heating to 800 ℃ at the speed of 15 ℃/min, and preserving heat for 3h to carry out hydrogen reduction to obtain nano molybdenum powder doped with yttrium oxide nano particles; the doping oxidationIn the nano molybdenum powder of yttrium nano particles, the average particle size of the molybdenum powder is 70nm, and the average particle size of the doped yttrium oxide nano particles is 10 nm.
The surfactant in this example can also be one or more of PEG, PVP, and PVA in addition to PEG-1000.
Example 3
The embodiment comprises the following steps:
step one, ultrasonically dispersing commercial micron-sized molybdenum trioxide and carbon nano-particles in an ethanol solution under the assistance of a surfactant PVP, and then stirring and evaporating at 70 ℃ to dryness to obtain composite powder;
the commercial micron-sized molybdenum trioxide has an average particle size of 1.5 μm and a mass purity of 99.99%;
the average particle size of the carbon nano-particles is 20nm, the mass content of carbon in the carbon nano-particles is 99%, and the adding mass of the carbon nano-particles is 3.9% of the mass of commercial micron-sized molybdenum trioxide; the added mass of the surface active agent PVP is 0.3 percent of the total mass of the carbon nano particles and the commercial micron-sized molybdenum trioxide;
step two, ultrasonically atomizing 0.03g/mL yttrium nitrate solution into superfine/nano yttrium salt liquid drops by adopting an ultrasonic nano atomizer, then uniformly spraying the superfine/nano yttrium salt liquid drops into the composite powder obtained in the step one according to the proportion of adding 20mL yttrium nitrate solution into 100g of composite powder, and drying to obtain a mixture containing yttrium salt; the mass of yttrium salt in the sprayed superfine/nano yttrium salt liquid drop is 0.9 percent of the mass of molybdenum element in the composite powder; the atomization vibration frequency is 1.7MHz, and the average particle size of yttrium nitrate in the yttrium salt-containing mixture is 30 nm;
step three, sequentially preserving the yttrium salt-containing mixture obtained in the step two for 2 hours at the conditions of 530 ℃ for 3 hours and 590 ℃ to obtain the superfine doped MoO2(ii) a The ultra-fine doped MoO2Has an average particle size of 150 nm;
step four, the superfine doped MoO obtained in the step three is used2Laying until the thickness of the material layer is 10mm, then placing in a hydrogen atmosphere with the mass purity of 99.99 percent, adopting a programmed heating method, heating to 900 ℃ at the speed of 8 ℃/minPreserving the heat for 1h for hydrogen reduction to obtain nanometer molybdenum powder doped with yttrium oxide nanoparticles; in the yttrium oxide nanoparticle-doped molybdenum nano-powder, the average particle size of the molybdenum powder is 106nm, and the average particle size of the yttrium oxide nanoparticle-doped molybdenum powder is 30 nm.
The surfactant in this example may also be one or more of PEG, PVP, and PVA in addition to PVP.
Example 4
The embodiment comprises the following steps:
step one, ultrasonically dispersing commercial micron-sized molybdenum trioxide and carbon nano-particles in an ethanol solution with the aid of surfactants PVP and PEG-1000, and then stirring and evaporating at 70 ℃ to dryness to obtain composite powder;
the commercial micron-sized molybdenum trioxide has an average particle size of 5 μm and a mass purity of 99.6%;
the average particle size of the carbon nano-particles is 70nm, the mass content of carbon in the carbon nano-particles is 99%, and the adding mass of the carbon nano-particles is 4.1% of the mass of commercial micron-sized molybdenum trioxide; the adding mass of the surfactants PVP and PEG-1000 is 1.2 percent of the total mass of the carbon nano particles and the commercial micron-sized molybdenum trioxide, wherein the mass ratio of the PEG-1000 to the PVP is 7: 3;
step two, ultrasonically atomizing 0.2g/mL yttrium nitrate solution into superfine/nano yttrium salt liquid drops by adopting an ultrasonic nano atomizer, then uniformly spraying the superfine/nano yttrium salt liquid drops into the composite powder obtained in the step one according to the proportion of adding 10mL yttrium nitrate solution into 100g of composite powder, and drying to obtain a mixture containing yttrium salt; the mass of yttrium salt in the sprayed superfine/nano yttrium salt liquid drop is 3% of the mass of molybdenum element in the composite powder; the atomization vibration frequency is 0.2MHz, and the average particle size of yttrium nitrate in the yttrium salt-containing mixture is 50 nm;
step three, sequentially preserving the yttrium salt-containing mixture obtained in the step two for 4 hours at the temperature of 520 ℃ and 560 ℃ to obtain the superfine doped MoO2(ii) a The ultra-fine doped MoO2Has an average particle size of 93 nm;
step four, the superfine doped MoO obtained in the step three is used2Laying until the thickness of a material layer is 25mm, then placing the material layer in a hydrogen atmosphere with the mass purity of 99.99 percent, adopting a programmed heating method, heating to 900 ℃ at the speed of 5 ℃/min, and preserving heat for 2h to carry out hydrogen reduction to obtain nano molybdenum powder doped with yttrium oxide nano particles; in the yttrium oxide nanoparticle-doped molybdenum nano-powder, the average particle size of the molybdenum powder is 160nm, and the average particle size of the yttrium oxide nanoparticle-doped molybdenum powder is 50 nm.
The surfactant in this example can also be one or more of PEG, PVP, and PVA in addition to the PEG-1000 and PVP combination.
Example 5
The embodiment comprises the following steps:
step one, ultrasonically dispersing commercial micron-sized molybdenum trioxide and carbon nanoparticles in an ethanol solution with the aid of a surfactant PEG, and then stirring and evaporating at 50 ℃ to dryness to obtain composite powder;
the commercial micron-sized molybdenum trioxide has an average particle size of 1 μm and a mass purity of 99.5%;
the average particle size of the carbon nano-particles is 10nm, the mass content of carbon in the carbon nano-particles is 99.5%, and the adding mass of the carbon nano-particles is 4.0% of the mass of commercial micron-sized molybdenum trioxide; the added mass of the surfactant PEG is 0.5 percent of the total mass of the carbon nano particles and the commercial micron-sized molybdenum trioxide;
step two, ultrasonically atomizing 0.01g/mL yttrium sulfate solution into superfine/nano yttrium salt liquid drops by adopting an ultrasonic nano atomizer, then uniformly spraying the superfine/nano yttrium salt liquid drops into the composite powder obtained in the step one according to the proportion of adding 15mL yttrium sulfate solution into 100g of composite powder, and drying to obtain a mixture containing yttrium salt; the mass of yttrium salt in the sprayed superfine/nano yttrium salt liquid drop is 0.3 percent of the mass of molybdenum element in the composite powder; the atomization vibration frequency is 2.4MHz, and the average particle size of yttrium sulfate in the yttrium salt-containing mixture is 10 nm;
step three, sequentially preserving the yttrium salt-containing mixture obtained in the step two for 2 hours at the conditions of 530 ℃ for 3 hours and 560 ℃ to obtain the superfine doped MoO2(ii) a The ultra-fine doped MoO2Average of (2)The particle size is 115 nm;
step four, the superfine doped MoO obtained in the step three is used2Laying until the thickness of a material layer is 5mm, then placing the material layer in a hydrogen atmosphere with the mass purity of 99.99 percent, adopting a programmed heating method, heating to 800 ℃ at the speed of 15 ℃/min, and preserving heat for 2h to carry out hydrogen reduction to obtain nano molybdenum powder doped with yttrium oxide nano particles; in the yttrium oxide nanoparticle-doped molybdenum nano-powder, the average particle size of the molybdenum powder is 60nm, and the average particle size of the yttrium oxide nanoparticle-doped molybdenum powder is 10 nm.
The surfactant in this example can also be one or more of PEG, PVP, and PVA in addition to PEG.
Example 6
The embodiment comprises the following steps:
step one, ultrasonically dispersing commercial micron-sized molybdenum trioxide and carbon nano-particles in an ethanol solution with the aid of a surfactant PVP, and then stirring and evaporating at 60 ℃ to dryness to obtain composite powder;
the commercial micron-sized molybdenum trioxide has an average particle size of 1 μm and a mass purity of 99.5%;
the average particle size of the carbon nano-particles is 20nm, the mass content of carbon in the carbon nano-particles is 99%, and the adding mass of the carbon nano-particles is 4.1% of the mass of commercial micron-sized molybdenum trioxide; the added mass of the surface active agent PVP is 0.2 percent of the total mass of the carbon nano particles and the commercial micron-sized molybdenum trioxide;
step two, ultrasonically atomizing 0.015g/mL yttrium nitrate solution into superfine/nano yttrium salt liquid drops by adopting an ultrasonic nano atomizer, then uniformly spraying the superfine/nano yttrium salt liquid drops into the composite powder obtained in the step one according to the proportion of adding 20mL yttrium nitrate solution into 100g of composite powder, and drying to obtain a mixture containing yttrium salt; the mass of yttrium salt in the sprayed superfine/nano yttrium salt liquid drop is 0.45 percent of the mass of molybdenum element in the composite powder; the atomization vibration frequency is 1.7MHz, and the average particle size of yttrium nitrate in the yttrium salt-containing mixture is 15 nm;
step three, the yttrium salt-containing mixture obtained in the step two is sequentially subjected to heat preservation at 530 ℃ for 3h and at 580 DEG CKeeping the temperature for 2 hours to obtain the superfine doped MoO2(ii) a The ultra-fine doped MoO2Has an average particle size of 160 nm;
step four, the superfine doped MoO obtained in the step three is used2Laying until the thickness of a material layer is 12mm, then placing the material layer in a hydrogen atmosphere with the mass purity of 99.99 percent, adopting a programmed heating method, heating to 850 ℃ at the speed of 10 ℃/min, and preserving heat for 2h to carry out hydrogen reduction to obtain nano molybdenum powder doped with yttrium oxide nano particles; in the yttrium oxide nanoparticle-doped molybdenum nano-powder, the average particle size of the molybdenum powder is 87nm, and the average particle size of the yttrium oxide nanoparticle-doped molybdenum powder is 15 nm.
The surfactant in this example may also be one or more of PEG, PVP, and PVA in addition to PVP.
Example 7
The embodiment comprises the following steps:
step one, ultrasonically dispersing commercial micron-sized molybdenum trioxide and carbon nano-particles in an ethanol solution with the aid of a surfactant PEG-1000, and then stirring and evaporating at 65 ℃ to dryness to obtain composite powder;
the commercial micron-sized molybdenum trioxide has an average particle size of 1 μm and a mass purity of 99.5%;
the average particle size of the carbon nano-particles is 20nm, the mass content of carbon in the carbon nano-particles is 99%, and the adding mass of the carbon nano-particles is 4.0% of the mass of commercial micron-sized molybdenum trioxide; the added mass of the surfactant PEG-1000 is 0.2 percent of the total mass of the carbon nano particles and the commercial micron-sized molybdenum trioxide;
step two, ultrasonically atomizing 0.01g/mL yttrium nitrate solution into superfine/nano yttrium salt liquid drops by adopting an ultrasonic nano atomizer, then uniformly spraying the superfine/nano yttrium salt liquid drops into the composite powder obtained in the step one according to the proportion of adding 5mL yttrium nitrate solution into 100g of composite powder, and drying to obtain a mixture containing yttrium salt; the mass of yttrium nitrate in the sprayed superfine/nano yttrium salt liquid drop is 0.05 percent of the mass of molybdenum element in the composite powder; the atomization vibration frequency is 1.7MHz, and the average particle size of yttrium nitrate in the yttrium salt-containing mixture is 13 nm;
step three, sequentially preserving the yttrium salt-containing mixture obtained in the step two for 2 hours at the conditions of 530 ℃ for 3 hours and 560 ℃ to obtain the superfine doped MoO2(ii) a The ultra-fine doped MoO2Has an average particle size of 140 nm;
step four, the superfine doped MoO obtained in the step three is used2Laying until the thickness of a material layer is 15mm, then placing the material layer in a hydrogen atmosphere with the mass purity of 99.999 percent, adopting a programmed heating method, heating to 750 ℃ at the speed of 20 ℃/min, and preserving heat for 3h to carry out hydrogen reduction to obtain nano molybdenum powder doped with yttrium oxide nano particles; in the yttrium oxide nanoparticle-doped molybdenum nano-powder, the average particle size of the molybdenum powder is 86nm, and the average particle size of the yttrium oxide nanoparticle-doped molybdenum powder is 13 nm.
The surfactant in this example can also be one or more of PEG, PVP, and PVA in addition to PEG-1000.
The application of the yttrium oxide nanoparticle-doped nano molybdenum powder of the present invention is described in detail in examples 8 to 9.
Example 8
The specific process applied in the embodiment is as follows: the yttrium oxide nanoparticle-doped nano molybdenum powder prepared in example 1 is sintered for 10min at 1100 ℃ under 40MPa by spark plasma sintering (SPS sintering), and the nano-structured yttrium oxide dispersion-strengthened ultrafine-grained molybdenum alloy with the density of 97% is prepared.
Example 9
The specific process applied in the embodiment is as follows: the yttrium oxide nanoparticle-doped molybdenum nanopowder prepared in example 5 was sintered by Spark Plasma Sintering (SPS) at 1000 ℃ and 60MPa for 10min to prepare an ultra-fine grained molybdenum alloy with nanostructure yttrium oxide dispersion-strengthened, which has a density of 97.3%.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modification, change and equivalent changes of the above embodiments according to the technical essence of the invention are still within the protection scope of the technical solution of the invention.
Claims (8)
1. A preparation method of nanometer molybdenum powder doped with yttrium oxide nanoparticles is characterized by comprising the following steps:
step one, ultrasonically dispersing commercial micron-sized molybdenum trioxide and carbon nano-particles in an ethanol solution with the aid of a surfactant, and then stirring and evaporating to dryness to obtain composite powder; the average particle size of the carbon nano-particles is 10-70 nm, the mass content of carbon in the carbon nano-particles is more than 98%, and the adding mass of the carbon nano-particles is 3.9-4.1% of the mass of commercial micron-sized molybdenum trioxide;
step two, carrying out ultrasonic atomization on an yttrium salt solution to form ultrafine nano yttrium salt liquid drops, then uniformly spraying the ultrafine nano yttrium salt liquid drops into the composite powder obtained in the step one, and drying to obtain a mixture containing yttrium salt; the average particle size of yttrium salt in the mixture containing yttrium salt is 10 nm-50 nm;
step three, respectively preserving the heat of the yttrium-containing salt mixture obtained in the step two for 2 to 4 hours at the temperature of 520 to 540 ℃ and the temperature of 560 to 590 ℃ in sequence to obtain the superfine doped MoO2；
Step four, the superfine doped MoO obtained in the step three is used2And (3) carrying out hydrogen reduction after laying to obtain the nano molybdenum powder doped with yttrium oxide nano particles.
2. The method for preparing nano molybdenum powder doped with yttrium oxide nano particles according to claim 1, wherein the commercial micron molybdenum trioxide in the first step has an average particle size of 1 μm to 5 μm and a mass purity of not less than 99.5%.
3. The method for preparing nano molybdenum powder doped with yttrium oxide nano particles according to claim 1, wherein the surfactant is one or more of PEG, PVP and PVA in the step one, and the added mass of the surfactant is 0.2-1.2% of the total mass of the carbon nano particles and the commercial micron-sized molybdenum trioxide.
4. The method for preparing yttrium oxide nanoparticle-doped nano molybdenum powder according to claim 1, wherein in the second step, the yttrium salt solution is yttrium soluble nitrate or sulfate, the concentration of the yttrium salt solution is 0.01 g/mL-0.2 g/mL, and the mass of yttrium salt in the sprayed superfine nano yttrium salt liquid drop is 0.05-3% of the mass of molybdenum element in the composite powder; the vibration frequency of the atomization is 0.2 MHz-2.5 MHz.
5. The method for preparing nano molybdenum powder doped with yttrium oxide nano particles according to claim 1, wherein the temperature of hydrogen reduction in the fourth step is 750-900 ℃, and the holding time is 1-3 h.
6. The method for preparing nano molybdenum powder doped with yttrium oxide nano particles according to claim 1, wherein in the fourth step, the hydrogen reduction adopts a programmed heating method, and the heating rate is 5 ℃/min to 20 ℃/min; the mass purity of the hydrogen atmosphere is more than 99.9 percent, and the superfine doped MoO2The thickness of the laid material layer is 5 mm-25 mm.
7. The method according to claim 1, wherein in the step four, the molybdenum powder doped with yttrium oxide nanoparticles has an average particle size of 60nm to 160nm, and the doped yttrium oxide nanoparticles have an average particle size of 10nm to 50 nm.
8. Use of a nano-molybdenum powder doped with yttrium oxide nanoparticles, prepared by a method according to any one of claims 1 to 7, to prepare a nanostructured oxide dispersion strengthened molybdenum alloy by sintering the nano-molybdenum powder doped with yttrium oxide nanoparticles.
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