CN115323212A - Preparation method of ultrafine molybdenum powder and molybdenum alloy with oxide nanoparticles distributed in crystal - Google Patents
Preparation method of ultrafine molybdenum powder and molybdenum alloy with oxide nanoparticles distributed in crystal Download PDFInfo
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- C22C32/0015—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides with only single oxides as main non-metallic constituents
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Abstract
The invention discloses a method for preparing superfine molybdenum powder and molybdenum alloy with oxide nano particles distributed in crystals, which comprises the following steps: 1. carrying out surface modification treatment and void structure regulation treatment on the molybdenum dioxide nano composite powder to obtain molybdenum dioxide nano composite powder with a high void structure; 2. processing and dispersing the enhanced phase precursor salt solution to obtain aerosol containing superfine liquid drops; 3. mixing aerosol containing superfine liquid drops into the molybdenum dioxide nano composite powder with a high pore structure; 4. drying; 5. high-temperature hydrogen treatment; 6. and (5) sintering. According to the invention, an enhanced phase precursor nano-salt composite structure is constructed on the surface of the molybdenum dioxide nano-composite powder particles, a molybdenum source is directionally transmitted and migrated to the surface of the oxide nano-particles for reduction and deposition growth by combining high-temperature hydrogen treatment, and the oxide nano-particles are coated in the molybdenum particles, so that the control of the particle size, uniformity and dispersibility of the molybdenum powder and the distribution of the oxide nano-enhanced phase in the molybdenum particles is realized.
Description
Technical Field
The invention belongs to the technical field of powder material preparation, and particularly relates to a method for preparing ultrafine molybdenum powder and molybdenum alloy with oxide nanoparticles distributed in crystals.
Background
Molybdenum has a number of excellent properties, such as: has high melting point, high strength and high elastic modulus, low expansion coefficient, good electric conductivity and thermal conductivity, excellent corrosion resistance and the like. By virtue of the excellent characteristics, the molybdenum material becomes one of the most widely applied refractory metals at present, and has important application in the fields of aviation, aerospace, electronics, military, chemistry, nuclear energy, metallurgy and the like. Because the melting point of molybdenum is high, the powder metallurgy method becomes the main method for preparing molybdenum materials at present, molybdenum powder is the most key basic raw material, and the characteristics of the particle size and the like of the molybdenum powder have great influence on the preparation process, the tissue structure and the performance of subsequent molybdenum products. In recent years, with the rapid development of the industries such as aerospace, military, chemistry, nuclear energy, metallurgy and the like, higher requirements are placed on the properties of molybdenum and the alloy materials thereof. The molybdenum material with a common structure is difficult to meet the requirements of high-performance molybdenum-based alloy micro-nano structure design and performance improvement. Numerous researches show that the performance of the molybdenum material with the ultra-fine grain nano structure is improved to show great advantages and become an important development trend of the molybdenum material.
The granularity, uniformity, dispersibility and reinforced phase composite structure of the molybdenum powder determine the sintering process, the texture structure and the performance of the molybdenum powder. Therefore, the ultrafine granularity of the molybdenum powder and the design and the regulation of the nano-scale configuration of the reinforcing phase become the key for preparing the molybdenum material with the high-performance ultrafine-grained nano-structure. Many researchers regulate and control the structure of the molybdenum and reinforced phase (carbide, boride, carbide and the like) composite powder by solid-phase compounding, solid-liquid compounding and liquid-liquid compounding, but the control of the granularity, uniformity, dispersibility, reinforced phase nanocrystallization and intra-crystal distribution of the molybdenum powder is difficult to realize.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide a method for preparing ultrafine molybdenum powder and molybdenum alloy with oxide nanoparticles distributed in the crystal aiming at the defects of the prior art. The method comprises the steps of mixing aerosol of enhanced phase precursor salt solution into molybdenum dioxide nano composite powder with a high-porosity structure, constructing an enhanced phase precursor nano salt composite structure on the surface of molybdenum dioxide nano composite powder particles, combining high-temperature hydrogen treatment to enable a molybdenum source to be directionally transmitted and migrated to the surface of oxide nano particles for reduction and deposition growth, and coating the oxide nano particles in the molybdenum particles, so that the control of the granularity, uniformity and dispersibility of the molybdenum powder and the distribution of oxide nano enhanced phases in the molybdenum particles is realized.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: the preparation method of the ultrafine molybdenum powder and the molybdenum alloy with oxide nano particles distributed in the crystal is characterized in that molybdenum dioxide nano composite powder is used as a molybdenum source, the molybdenum source is firstly subjected to surface modification treatment and void structure regulation treatment, and then soluble salt is used as a reinforcing phase precursor to be compounded in an aerosol mode; the method comprises the following steps:
step one, carrying out surface modification treatment and void structure regulation treatment on molybdenum dioxide nano composite powder to obtain high-void structure molybdenum dioxide nano composite powder;
secondly, processing and dispersing the enhanced phase precursor salt solution through high-frequency electronic oscillation to obtain aerosol containing superfine liquid drops;
step three, mixing the aerosol containing the superfine liquid drops obtained in the step two into the molybdenum dioxide nano composite powder with the high pore structure obtained in the step one to obtain the molybdenum dioxide nano composite powder with the micro-nano salt liquid drops attached to the surface;
step four, drying the molybdenum dioxide nano composite powder with the surface attached with the micro-nano salt liquid drops obtained in the step three to obtain the molybdenum dioxide nano composite powder with the surface attached with the nano salt particles;
fifthly, carrying out high-temperature hydrogen treatment on the molybdenum dioxide nano composite powder with the surface attached with the nano salt particles obtained in the fourth step to obtain superfine molybdenum powder with oxide nano particles distributed in crystal;
and step six, sintering the ultrafine molybdenum powder with the oxide nanoparticles distributed in the crystal obtained in the step five to obtain the ultrafine crystal molybdenum alloy with the oxide nanoparticles distributed in the crystal.
The method comprises the steps of taking molybdenum dioxide nano composite powder and enhanced phase precursor salt solution as raw materials, firstly carrying out surface modification treatment and gap structure regulation treatment on the molybdenum dioxide nano composite powder to convert the molybdenum dioxide nano composite powder into molybdenum dioxide nano composite powder with a high-pore structure, carrying out high-frequency electronic oscillation treatment and dispersion on the enhanced phase precursor salt solution to convert the enhanced phase precursor salt solution into aerosol containing ultrafine liquid drops, then mixing the two to ensure that the aerosol containing ultrafine liquid drops is uniformly adsorbed on the surface of the molybdenum dioxide nano composite powder with the high-pore structure, drying to ensure that the water of the micro-nano liquid drops is evaporated and the nano salt particles are separated out, thereby constructing an enhanced phase precursor nano salt composite structure on the surface of the molybdenum dioxide nano composite powder particles, and further carrying out high-temperature hydrogen treatment to ensure that the nano salt particles are decomposed into oxide nano particles on the one hand, and on the other hand, utilizing a molybdenum-containing gas-phase hydrate generated in a hydrogen atmosphere to ensure that a molybdenum source is directionally transported and transferred to the surface of the oxide nano particles in a gas phase manner to carry out reduction and deposition growth, so that the oxide nano particles are coated in the molybdenum particles, and the interior of the molybdenum powder, thereby realizing the particle size, uniformity, the dispersibility and the control of the distribution of the enhanced phase of the molybdenum particles.
The preparation method of the ultrafine molybdenum powder and the molybdenum alloy with the oxide nanoparticles distributed in the crystal is characterized in that in the first step, the molybdenum dioxide nano composite powder contains molybdenum dioxide with the mass content of more than 80 percent and Mo with the mass content of less than 20 percent 4 O 11 Or nano molybdenum particles, and the average particle size of the molybdenum dioxide nano composite powder is less than 600nm; the surface modification treatment method is ultrasonic irradiation, mechanical friction or plasma treatment, and the gap structure regulation treatment method is ultrahigh-speed mechanical treatment; the porosity of the molybdenum dioxide nano composite powder with the high-porosity structure is more than 80 percent.
The preparation method of the ultrafine molybdenum powder and the molybdenum alloy with the oxide nanoparticles distributed in the crystal is characterized in that the frequency of the high-frequency electronic oscillation in the step two is more than 1.5MHz, the salt solution of the enhanced phase precursor is a soluble salt solution of ceramic or rare earth, and the mass concentration of the solution is less than 0.3g/mL; the aerosol containing the ultrafine droplets has a particle size of less than 10 μm.
The preparation method of the ultrafine molybdenum powder and the molybdenum alloy with the oxide nanoparticles distributed in the crystal is characterized in that the mixing mass of the aerosol containing ultrafine liquid drops in the third step is less than 30% of that of the molybdenum dioxide nano composite powder in the first step.
The preparation method of the ultrafine molybdenum powder and the molybdenum alloy with the oxide nanoparticles distributed in the crystal is characterized in that the average particle size of the nano salt particles in the molybdenum dioxide nano composite powder with the nano salt particles attached to the surface is less than 40nm in the fourth step.
The preparation method of the ultrafine molybdenum powder and molybdenum alloy with the oxide nanoparticles distributed in the crystal is characterized in that the temperature of the high-temperature hydrogen treatment in the fifth step is 750-950 ℃, the volume fraction of the adopted hydrogen is more than 90%, and the dew point of the hydrogen is more than-40 ℃; the average particle size of molybdenum grains in the ultrafine molybdenum powder with the oxide nano-particles distributed in the grains is less than 500nm, the average particle size of the oxide nano-particles distributed in the molybdenum grains is less than 20nm, and the mass of the oxide nano-particles is less than 3% of that of the molybdenum grains.
The preparation method of the ultrafine molybdenum powder with the oxide nano particles distributed in the crystal and the molybdenum alloy is characterized in that the sintering mode in the sixth step is vacuum SPS sintering or pressureless hydrogen sintering, the density of the ultrafine crystal molybdenum alloy with the oxide nano particles distributed in the crystal is more than 97 percent, the average grain size of the molybdenum alloy crystal grains is less than 3 mu m, and the average grain size of the oxide nano particles distributed in the molybdenum alloy crystal grains is less than 50nm.
Compared with the prior art, the invention has the following advantages:
1. the molybdenum dioxide nano composite powder is used as a molybdenum source, has higher specific surface area compared with common molybdenum dioxide, is easier to prepare and obtain compared with single-phase molybdenum dioxide, and contains a small amount of Mo 4 O 11 Or the nano molybdenum particles inhibit the coalescence growth of the molybdenum dioxide at high temperature, and improve the dispersibility of the molybdenum dioxide, and meanwhile, the surface modification treatment is adopted to increase the defects of the surface of the molybdenum dioxide, thereby improving the activity of the molybdenum dioxide and creating the adhesion of the subsequent aerosolAnd (4) making conditions.
2. The invention adopts the ultra-high speed mechanical treatment method to improve the dispersibility and the void ratio of the molybdenum dioxide nano composite powder, improves the void ratio to be more than 80 percent, even to be more than 90 percent, is obviously superior to the common molybdenum dioxide, and provides basic conditions for uniform diffusion and transmission after the aerosol containing ultrafine liquid drops is mixed in the material layer.
3. The method takes soluble enhanced phase precursor salt as a raw material, atomizes a salt solution thereof into aerosol by adopting a high-frequency electronic oscillation mode, and then introduces the aerosol into the molybdenum dioxide with a high-porosity structure, so that the aerosol containing superfine liquid drops is uniformly adsorbed on the surface of the molybdenum dioxide nano composite powder with the high-porosity structure, and nano salt particles are separated out after drying, and the average particle size of the nano salt particles can be less than 10nm at least, and the particle size is controllable, so that the method is obviously superior to the traditional doping method.
4. According to the invention, an enhanced phase precursor nano-salt composite structure is constructed on the surface of the molybdenum dioxide nano-composite powder particles, and then a molybdenum-containing gas phase hydrate generated in a hydrogen atmosphere is utilized to directionally transmit a molybdenum source to the vicinity of the enhanced phase oxide nano-particles for reduction and deposition growth, so that the enhanced phase particles are coated inside the molybdenum particles, the control of the distribution of the nano-enhanced phase inside the molybdenum particles is realized, and the average particle size of the enhanced phase of the oxide nano-particles can reach below 10 nm.
5. The invention takes ultrafine molybdenum powder with oxide nano particles distributed in the crystal as a raw material, and obtains the high-density ultrafine crystal molybdenum alloy with the oxide nano particles distributed in the crystal through low-temperature sintering, wherein the particle size of the enhanced phase oxide nano particles distributed in the molybdenum crystal grains is less than 50nm.
The technical solution of the present invention is further described in detail by the accompanying drawings and examples.
Drawings
FIG. 1 is an SEM image of an ultrafine molybdenum powder with alumina nanoparticles distributed in the crystal prepared in example 1 of the present invention.
FIG. 2 is a TEM image of the ultra-fine molybdenum powder with alumina nanoparticles distributed in the crystal, prepared in example 1 of the present invention.
FIG. 3 is a TEM image of an ultra-fine grained molybdenum alloy with alumina nanoparticles distributed in the crystal prepared in example 1 of the present invention.
Detailed Description
Example 1
The embodiment comprises the following steps:
step one, carrying out surface modification treatment and void structure regulation treatment on molybdenum dioxide nano composite powder to obtain high-void structure molybdenum dioxide nano composite powder; the molybdenum dioxide nano composite powder contains 95% by mass of molybdenum dioxide and 5% by mass of nano molybdenum particles, and the average particle size of the molybdenum dioxide nano composite powder is 300nm; the surface modification treatment method is ultrasonic irradiation, the gap structure regulation treatment method is ultra-high-speed mechanical stirring treatment, the rotating speed is 2 ten thousand revolutions per minute, and the treatment time is 240s; the porosity of the molybdenum dioxide nano composite powder with the high-porosity structure is 90 percent;
step two, processing and dispersing the enhanced phase precursor salt solution through high-frequency electronic oscillation to obtain aerosol containing superfine liquid drops; the frequency of the high-frequency electronic oscillation is 2.5MHz, the enhanced phase precursor salt solution is an aluminum nitrate solution, and the mass concentration of the enhanced phase precursor salt solution is 0.084g/mL; the particle size of the aerosol containing the superfine liquid drops is 3 mu m;
step three, mixing the aerosol containing the ultrafine liquid drops obtained in the step two into the molybdenum dioxide nano composite powder with the high pore structure obtained in the step one to obtain the molybdenum dioxide nano composite powder with the micro-nano salt liquid drops attached to the surface; the mixing mass of the aerosol containing the superfine liquid drops is 20 percent of the mass of the molybdenum dioxide nano composite powder in the step one;
step four, drying the molybdenum dioxide nano composite powder with the surface attached with the micro-nano salt droplets obtained in the step three to obtain molybdenum dioxide nano composite powder with the surface attached with nano salt particles; the average particle size of the nano salt particles in the molybdenum dioxide nano composite powder with the nano salt particles attached to the surface is 10nm;
step five, performing high-temperature hydrogen treatment on the molybdenum dioxide nano composite powder with the surface attached with the nano salt particles obtained in the step four to obtain ultrafine molybdenum powder with alumina nano particles distributed in the crystal, wherein SEM images and TEM images are respectively shown in figures 1 and 2, and arrows in figure 2 indicate the alumina nano particles; the temperature of the high-temperature hydrogen treatment is 750-850 ℃, the volume fraction of the adopted hydrogen is 99.9%, and the dew point of the hydrogen is-35 ℃; the average particle size of molybdenum grains in the ultrafine molybdenum powder with the alumina nano-particles distributed in the grains is 90nm, the average particle size of the alumina nano-particles distributed in the molybdenum grains is 7.5nm, and the mass of the alumina nano-particles is 0.5 percent of that of the molybdenum grains;
step six, sintering the superfine molybdenum powder with the alumina nano particles distributed in the crystal obtained in the step five by using a sintering vacuum SPS (spark plasma sintering) at the sintering temperature of 1100 ℃ to obtain the superfine crystal molybdenum alloy with the alumina nano particles distributed in the crystal, wherein a TEM (transmission electron microscope) image of the superfine crystal molybdenum alloy is shown in figure 3, and arrows in figure 3 indicate the alumina nano particles; the density of the ultrafine grain molybdenum alloy with alumina nano-particles distributed in the grain is 98.7 percent, the average grain size of the molybdenum alloy grain is 480nm, and the average grain size of the alumina nano-particles distributed in the molybdenum alloy grain is 19nm.
The method of surface modification treatment in this embodiment may also be replaced with mechanical friction or plasma treatment.
Example 2
The present embodiment differs from example 1 in that: in the second step, the enhanced phase precursor salt solution is an aluminum nitrate solution, and the mass concentration of the enhanced phase precursor salt solution is 0.168g/mL; in the fourth step, the average particle size of the nano salt particles in the molybdenum dioxide nano composite powder with the nano salt particles attached to the surface is 15nm; in the fifth step, the average particle size of molybdenum grains in the ultrafine molybdenum powder with the alumina nano-particles distributed in the grains is 80nm, the average particle size of the alumina nano-particles distributed in the molybdenum grains is 12nm, and the mass of the alumina nano-particles is 1.0 percent of that of the molybdenum grains; in the sixth step, the density of the ultrafine grain molybdenum alloy with alumina nano-particles distributed in the grains is 98.5 percent, the average grain size of the molybdenum alloy grains is 400nm, and the average grain size of the alumina nano-particles distributed in the molybdenum alloy grains is 25nm.
Example 3
The embodiment comprises the following steps:
step one, carrying out surface modification treatment on molybdenum dioxide nano composite powder andregulating and controlling the void structure to obtain the molybdenum dioxide nano composite powder with a high void structure; the molybdenum dioxide nano composite powder contains 98 mass percent of molybdenum dioxide and 2 mass percent of Mo 4 O 11 And the average particle size of the molybdenum dioxide nano composite powder is 300nm; the surface modification treatment method is ultrasonic irradiation, the gap structure regulation treatment method is ultra-high speed mechanical stirring treatment, and the rotating speed is 1.5 ten thousand revolutions per minute; the porosity of the molybdenum dioxide nano composite powder with the high-porosity structure is 85 percent;
step two, processing and dispersing the enhanced phase precursor salt solution through high-frequency electronic oscillation to obtain aerosol containing superfine liquid drops; the frequency of the high-frequency electronic oscillation is 1.7MHz, the enhanced phase precursor salt solution is yttrium nitrate solution, and the mass concentration is 0.05g/mL; the particle size of the liquid drops in the aerosol containing the superfine liquid drops is 3 mu m;
step three, mixing the aerosol containing the ultrafine liquid drops obtained in the step two into the molybdenum dioxide nano composite powder with the high pore structure obtained in the step one to obtain the molybdenum dioxide nano composite powder with the micro-nano salt liquid drops attached to the surface; the mixing mass of the aerosol containing the superfine liquid drops is 15% of that of the molybdenum dioxide nano composite powder in the first step;
step four, drying the molybdenum dioxide nano composite powder with the surface attached with the micro-nano salt liquid drops obtained in the step three to obtain the molybdenum dioxide nano composite powder with the surface attached with the nano salt particles; the average particle size of the nano salt particles in the molybdenum dioxide nano composite powder with the nano salt particles attached to the surface is 8.5nm;
step five, performing high-temperature hydrogen treatment on the molybdenum dioxide nano composite powder with the surface attached with the nano salt particles obtained in the step four to obtain superfine molybdenum powder with the yttrium oxide nano particles distributed in the crystal; the high-temperature hydrogen treatment temperature is 800-950 ℃, the volume fraction of the adopted hydrogen is 99.9%, and the dew point of the hydrogen is-30 ℃; the average particle size of molybdenum grains in the ultrafine molybdenum powder with the yttrium oxide nano-particles distributed in the grains is 65nm, the average particle size of the yttrium oxide nano-particles distributed in the molybdenum grains is 6.2nm, and the mass of the yttrium oxide nano-particles is 0.5 percent of that of the molybdenum grains;
step six, performing vacuum SPS sintering on the ultrafine molybdenum powder distributed with the yttrium oxide nano particles in the crystal obtained in the step five, wherein the sintering temperature is 1100 ℃, and obtaining the ultrafine crystal molybdenum alloy distributed with the yttrium oxide nano particles in the crystal; the density of the ultrafine grain molybdenum alloy with the yttrium oxide nano-particles distributed in the grain is 98.5%, the average grain size of the molybdenum alloy grain is 400nm, and the average grain size of the yttrium oxide nano-particles distributed in the molybdenum alloy grain is 21nm.
The method of surface modification treatment in this embodiment may also be replaced with mechanical friction or plasma treatment, and the sintering manner may also be replaced with pressureless hydrogen sintering.
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 modifications, alterations 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 (7)
1. The preparation method of the ultrafine molybdenum powder and the molybdenum alloy with oxide nano particles distributed in the crystal is characterized in that molybdenum dioxide nano composite powder is used as a molybdenum source, the molybdenum source is firstly subjected to surface modification treatment and void structure regulation treatment, and then soluble salt is used as a reinforcing phase precursor to be compounded in an aerosol mode; the method comprises the following steps:
step one, carrying out surface modification treatment and void structure regulation treatment on molybdenum dioxide nano composite powder to obtain high-void structure molybdenum dioxide nano composite powder;
step two, processing and dispersing the enhanced phase precursor salt solution through high-frequency electronic oscillation to obtain aerosol containing superfine liquid drops;
step three, mixing the aerosol containing the superfine liquid drops obtained in the step two into the molybdenum dioxide nano composite powder with the high pore structure obtained in the step one to obtain the molybdenum dioxide nano composite powder with the micro-nano salt liquid drops attached to the surface;
step four, drying the molybdenum dioxide nano composite powder with the surface attached with the micro-nano salt liquid drops obtained in the step three to obtain the molybdenum dioxide nano composite powder with the surface attached with the nano salt particles;
fifthly, carrying out high-temperature hydrogen treatment on the molybdenum dioxide nano composite powder with the surface attached with the nano salt particles obtained in the fourth step to obtain superfine molybdenum powder with oxide nano particles distributed in crystal;
and step six, sintering the ultrafine molybdenum powder with the oxide nanoparticles distributed in the crystal obtained in the step five to obtain the ultrafine crystal molybdenum alloy with the oxide nanoparticles distributed in the crystal.
2. The method for preparing the ultrafine molybdenum powder with the intragranular distributed oxide nanoparticles and the molybdenum alloy according to claim 1, wherein the molybdenum dioxide nanocomposite powder in the first step contains more than 80% by mass of molybdenum dioxide and less than 20% by mass of Mo 4 O 11 Or nano molybdenum particles, and the average particle size of the molybdenum dioxide nano composite powder is less than 600nm; the surface modification treatment method is ultrasonic irradiation, mechanical friction or plasma treatment, and the gap structure regulation treatment method is ultrahigh-speed mechanical treatment; the porosity of the molybdenum dioxide nano composite powder with the high-porosity structure is more than 80 percent.
3. The method for preparing the ultrafine molybdenum powder and the molybdenum alloy with the intragranular distributed oxide nanoparticles according to claim 1, wherein the frequency of the high-frequency electronic oscillation in the second step is greater than 1.5MHz, the salt solution of the enhanced phase precursor is a soluble salt solution of ceramic or rare earth, and the mass concentration of the salt solution is less than 0.3g/mL; the aerosol containing the ultrafine droplets has a particle size of less than 10 μm.
4. The method for preparing the ultra-fine molybdenum powder and the molybdenum alloy with the intragranular distributed oxide nanoparticles as claimed in claim 1, wherein the mixing mass of the aerosol containing the ultra-fine droplets in the third step is less than 30% of the mass of the molybdenum dioxide nanocomposite powder in the first step.
5. The method for preparing the ultrafine molybdenum powder and the molybdenum alloy with the intragranular oxide nanoparticles distributed therein according to claim 1, wherein the average particle size of the nanoparticles in the molybdenum dioxide nanocomposite powder with the nanoparticles attached to the surface thereof in the fourth step is less than 40nm.
6. The method for preparing the ultrafine molybdenum powder and the molybdenum alloy with the oxide nanoparticles distributed in the crystal according to claim 1, wherein the temperature of the high-temperature hydrogen treatment in the fifth step is 750-950 ℃, the volume fraction of the adopted hydrogen is more than 90%, and the dew point of the hydrogen is more than-40 ℃; the average particle size of molybdenum grains in the ultrafine molybdenum powder with the oxide nano-particles distributed in the grains is less than 500nm, the average particle size of the oxide nano-particles distributed in the molybdenum grains is less than 20nm, and the mass of the oxide nano-particles is less than 3% of that of the molybdenum grains.
7. The method for preparing ultra-fine molybdenum powder and molybdenum alloy with distributed oxide nanoparticles in the crystal as claimed in claim 1, wherein the sintering mode in step six is vacuum SPS sintering or pressureless hydrogen sintering, the density of the ultra-fine molybdenum alloy with distributed oxide nanoparticles in the crystal is more than 97%, the average particle size of the molybdenum alloy crystal grains is less than 3 μm, and the average particle size of the oxide nanoparticles distributed in the molybdenum alloy crystal grains is less than 50nm.
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| JPS5638445A (en) * | 1979-09-07 | 1981-04-13 | Tokyo Tungsten Co Ltd | Molybdenum material prepared by powder metallurgy |
| US20110223054A1 (en) * | 2008-10-17 | 2011-09-15 | H.C. Starck Inc. | Production of molybdenum metal powder |
| CN103286317A (en) * | 2013-06-30 | 2013-09-11 | 金堆城钼业股份有限公司 | Method for preparing molybdenum powder by ammonium molybdate |
| CN103409652A (en) * | 2013-07-12 | 2013-11-27 | 上海川禾实业发展有限公司 | Method for preparing molybdenum alloy material from molybdenum oxide surface modified modified metal powder |
| CN106363166A (en) * | 2016-09-12 | 2017-02-01 | 厦门理工学院 | Composite powder formed by uniformly doping nano-La2O3 in nano-Mo and preparation method thereof |
| CN112222419A (en) * | 2020-12-07 | 2021-01-15 | 西安稀有金属材料研究院有限公司 | Method for preparing nano molybdenum powder by regulating nucleation and growth processes and application |
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| JP5638445B2 (en) * | 2011-04-14 | 2014-12-10 | パイロットインキ株式会社 | Solid cursive and solid cursive set using the same |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5638445A (en) * | 1979-09-07 | 1981-04-13 | Tokyo Tungsten Co Ltd | Molybdenum material prepared by powder metallurgy |
| US20110223054A1 (en) * | 2008-10-17 | 2011-09-15 | H.C. Starck Inc. | Production of molybdenum metal powder |
| CN103286317A (en) * | 2013-06-30 | 2013-09-11 | 金堆城钼业股份有限公司 | Method for preparing molybdenum powder by ammonium molybdate |
| CN103409652A (en) * | 2013-07-12 | 2013-11-27 | 上海川禾实业发展有限公司 | Method for preparing molybdenum alloy material from molybdenum oxide surface modified modified metal powder |
| CN106363166A (en) * | 2016-09-12 | 2017-02-01 | 厦门理工学院 | Composite powder formed by uniformly doping nano-La2O3 in nano-Mo and preparation method thereof |
| CN112222419A (en) * | 2020-12-07 | 2021-01-15 | 西安稀有金属材料研究院有限公司 | Method for preparing nano molybdenum powder by regulating nucleation and growth processes and application |
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