CN115229202B - Preparation method of molybdenum-copper nano composite powder - Google Patents
Preparation method of molybdenum-copper nano composite powder Download PDFInfo
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Abstract
The invention discloses a preparation method of molybdenum-copper nano composite powder, which comprises the following steps: 1. mixing the raw materials uniformly; 2. heating the composite precursor; 3. ball milling, drying and stirring the mixture at a super high speed; 4. carrying out segmented heat treatment and ultrahigh-speed stirring on the molybdenum trioxide and carbon composite powder; 5. heating and stirring the two composite powders, dropwise adding superfine copper salt liquid drops, drying and stirring at ultrahigh speed; 6. and carrying out sectional heat treatment on the copper-containing mixed powder to obtain the molybdenum-copper nano composite powder with high dispersion and high porosity. According to the invention, copper salt is dissolved in ethanol and sprayed into the heated material, the solution is rapidly evaporated, the agglomeration of nano particles is avoided, the porosity of the material is increased, the nucleation rate of molybdenum powder is improved and the particle size of the product is refined by using high-activity amorphous carbon nano particles and copper salt nano particles, and then the nano molybdenum-copper composite powder is obtained by hydrogen reduction, and the particle size and the dispersibility of the copper nano particles and the composite powder are regulated and controlled.
Description
Technical Field
The invention belongs to the technical field of preparation of nano powder materials, and particularly relates to a preparation method of molybdenum-copper nano composite powder.
Background
Molybdenum-copper composites have a number of very excellent properties, such as: special high-temperature performance, good electric and thermal conductivity, corrosion resistance, low and adjustable thermal expansion coefficient, good processability and the like. By virtue of the excellent characteristics, the molybdenum-copper composite material has very critical application in many fields such as military industry, electronics and electrics, aerospace and the like. Because of the high melting point of molybdenum, sintering with molybdenum-copper composite powder as the main raw material is the main method for industrially preparing molybdenum-copper composite materials at present. The characteristics of the molybdenum-copper composite powder determine the temperature and time required for sintering and compacting, and then influence the microstructure (grain size) and performance of the composite material. The traditional process for preparing the molybdenum-copper composite powder is to mix copper powder and molybdenum powder according to a certain proportion and obtain the molybdenum-copper mixed powder by a mechanical grinding method, but the prepared molybdenum-copper composite powder has uneven components and is easy to introduce impurities, and the particle size of the powder is generally in a micron order (3-5 microns). Because the composite powder has large granularity, small specific surface area, and low surface activity and sintering activity, a compact sample can be obtained by sintering for a long time at a high sintering temperature of about 1600 ℃. Not only the sintering cost is higher, but also the prepared material has thick crystal grains, and the high-end application requirements are difficult to meet. The preparation of the nano molybdenum-copper powder with fine grains is the simplest and most effective shortcut for improving the sintering activity, reducing the sintering temperature and refining the grains. Therefore, the preparation of ultrafine-grained nanocrystalline alloy powder is a very critical first step in the preparation of fine-grained fully dense high-performance nano-alloys.
The molybdenum-copper composite powder is industrially prepared by taking molybdenum powder and copper powder as raw materials, wherein the characteristics (granularity) of the raw materials determine the sintering temperature and time, and then the microstructure (grain size) and the performance of a sintered product are influenced. The granularity and the shape of the molybdenum powder mainly depend on the stage of reducing molybdenum oxide by hydrogen, and at present, the conventional hydrogen reduces micron-sized high-purity MoO 3 Preparing micron-sized MoO 2 The process of re-reduction to molybdenum powder is difficult to control the nucleation and growth processes of the product, and the commercial molybdenum powder produced has a large particle size (about 2-5 microns). In addition, the traditional mechanical mixing mode of solid powder causes the problems of uneven dispersion of raw materials, large particle size difference and the like in the mixing process, and the prepared composite material has large grains and low performance. Therefore, the low-cost, simple and efficient preparation of the nano molybdenum-copper composite powder is still a difficult problem.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide a method for preparing molybdenum-copper nano composite powder, aiming at the defects of the prior art. The method combines the high-activity amorphous carbon nano-particles as a nucleating agent and a pore-forming agent for decomposing ammonium molybdate, effectively improves the molybdenum powder nucleation rate, controls the molybdenum nucleation and growth processes, refines the granularity of the product, obtains the nano molybdenum-copper composite powder by hydrogen reduction, and simultaneously realizes the granularity and dispersity regulation and control of the copper nano-particles and the composite powder.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a method for preparing molybdenum-copper nano composite powder is characterized by comprising the following steps:
adding amorphous carbon nano particles, ammonium molybdate, a surfactant and a pore-forming agent into deionized water, uniformly mixing, and drying to obtain a composite precursor;
step two, heating the composite precursor obtained in the step one to obtain a mixture of molybdenum trioxide and amorphous carbon nanoparticles;
step three, adding the mixture obtained in the step two into ethanol, then carrying out ball milling, and then sequentially carrying out drying and ultrahigh-speed stirring to obtain molybdenum trioxide and carbon composite powder;
step four, carrying out segmented heat treatment on the molybdenum trioxide and carbon composite powder obtained in the step three, and then carrying out ultrahigh-speed stirring to obtain molybdenum dioxide and molybdenum composite powder;
step five, heating and stirring the molybdenum dioxide and molybdenum composite powder obtained in the step four, then dropwise adding superfine copper salt liquid drops, drying and then carrying out ultrahigh-speed stirring to obtain copper-containing mixed powder; the preparation process of the superfine copper salt liquid drop comprises the following steps: dispersing copper salt into ethanol and carrying out ultrasonic atomization;
and step six, carrying out sectional heat treatment on the copper-containing mixed powder obtained in the step five in a hydrogen atmosphere to obtain the molybdenum-copper nano composite powder with high dispersion and high porosity.
According to the method, ammonium molybdate is used as a raw material, high-activity amorphous carbon nanoparticles are used as a nucleating agent for decomposing ammonium molybdate, a pore-forming agent is used as an assistant, firstly, a surfactant is used for dispersing the high-activity amorphous carbon nanoparticles in water and uniformly mixing the amorphous carbon nanoparticles with the ammonium molybdate, the mixing uniformity of the carbon nanoparticles and the ammonium molybdate is improved, then, a composite precursor is heated and decomposed, the carbon nanoparticles uniformly distributed in the ammonium molybdate provide a large number of heterogeneous nucleation points for amorphous cluster nucleation, so that the nucleation rate of molybdenum trioxide is improved, the steric hindrance is formed, the coalescence growth of molybdenum trioxide crystal nuclei is hindered, the particle size of the molybdenum trioxide is favorably reduced, in addition, part of the carbon nanoparticles are oxidized to generate a gas product in the decomposition process, the appearance and the particle size of the nano molybdenum trioxide are effectively ensured along with the increase of the porosity of gas escaping from the raw material, the agglomeration of the carbon nanoparticles is avoided, and the nano mixed powder with a loose structure is obtained; the method comprises the steps of performing two-stage heating pre-reduction on a mixture of molybdenum trioxide and amorphous carbon nanoparticles after ball milling and crushing as a precursor, inheriting the morphology and the granularity of molybdenum trioxide, and obtaining molybdenum dioxide and molybdenum composite powder, namely pre-reduction powder; uniformly spraying ultra-fine copper salt liquid drops subjected to ultrasonic atomization into heated pre-reduction powder, and drying and stirring at an ultrahigh speed to obtain nano copper-containing mixed powder; in the reduction process, copper salt nano particles are used as a nucleating agent to assist molybdenum nano particles to nucleate, the granularity of the molybdenum powder is further refined, and meanwhile, the copper salt is converted into the copper nano particles in situ, so that the molybdenum-copper nano composite powder is obtained.
The preparation method of the molybdenum-copper nano composite powder is characterized in that the average particle size of the amorphous carbon nano particles in the first step is more than 20nm, and the mass content of carbon in the amorphous carbon nano particles is more than 98%; the mass purity of the ammonium molybdate is more than 99.7 percent; the mass ratio of ammonium molybdate to water in the composite precursor is more than 0.1:1; the adding amount of the carbon nano particles is 5-10% of the mass of ammonium molybdate; the surfactant is one or more of polyvinyl alcohol, polyvinylpyrrolidone and polyethylene glycol, and the addition amount of the surfactant is 1-2% of the mass of ammonium molybdate; the pore-forming agent is glucose, sucrose or starch, and the addition amount of the pore-forming agent is 2-3% of the mass of ammonium molybdate. The carbon nano-particles with smaller granularity and excellent dispersion performance are used as a nucleating agent and a pore-forming agent in the decomposition process and the reduction process of ammonium molybdate, and the amorphous carbon nano-particles have higher reaction activity, so that the nucleation rate and the porosity of molybdenum are improved, the granularity of molybdenum powder is reduced, and the nano-molybdenum powder with a loose structure is obtained; the invention is beneficial to obtaining the mixed solution with excellent dispersivity of the carbon nano-particles and the ammonium molybdate by controlling the proportion of various raw materials; the invention is beneficial to avoiding the agglomeration of the carbon nano-particles and improving the mixing uniformity of the carbon nano-particles and the ammonium molybdate by controlling the components and the adding quality of the surfactant.
The preparation method of the molybdenum-copper nano composite powder is characterized in that the drying in the step one is rotary evaporation, wherein the temperature of the spray rotary evaporation is not less than 80 ℃, and the rotating speed is not less than 200r/min. According to the invention, the carbon nano-particles and ammonium molybdate in the prepared composite powder are fully dried and uniformly mixed by controlling the drying process and parameters.
The preparation method of the molybdenum-copper nano composite powder is characterized in that the heating treatment process in the step two is as follows: raising the temperature to 500-650 ℃ at a temperature raising rate of not less than 10 ℃/min, and then preserving the temperature for more than 2h, wherein the atmosphere of the heating treatment is air or oxygen. According to the invention, by controlling the parameters of the heating treatment, the fast heating rate is adopted, which is beneficial to improving the nucleation rate and the dispersibility of the molybdenum trioxide, the heat preservation temperature and the heat preservation time ensure that the ammonium molybdate is completely decomposed, and part of the carbon nano-particles fully react with air to form gaps, and the atmosphere can react with part of the carbon nano-particles in the composite powder to generate gas, so that the purpose of pore forming is achieved.
The preparation method of the molybdenum-copper nano composite powder is characterized in that the adding amount of ethanol in the third step is 60-80% of the mass of the mixture, the ball-to-material ratio in ball milling is not less than 2:1, the ball-milling rotating speed is not less than 200r/min, and the ball-milling time is not less than 2h. The invention ensures more sufficient ball milling by adding ethanol; the invention adopts larger ball-to-material ratio and faster ball-milling rotating speed, which is favorable for improving the mixing uniformity, reducing the particle size of powder particles and increasing the nucleation points of molybdenum trioxide.
The preparation method of the molybdenum-copper nano composite powder is characterized in that the rotation speed of ultrahigh-speed stirring in the third step, the fourth step and the fifth step is greater than 10000r/min, and the time is greater than 200s. The invention avoids the agglomeration of the nano powder by controlling the rotating speed and the time of the ultra-high speed stirring, and further increases the porosity of the mixed powder.
The preparation method of the molybdenum-copper nano composite powder is characterized in that the segmented heat treatment in the fourth step is as follows: firstly heating to 800-950 ℃, then preserving heat for more than 1h, then heating to 1000-1100 ℃, and preserving heat for more than 1h, wherein the atmosphere of the segmented heat treatment is argon atmosphere; the thickness of the molybdenum trioxide and carbon composite powder in the segmented heat treatment is not less than 10mm. The invention ensures the molybdenum oxide to react completely by controlling the parameters of the sectional heat treatment and adopting higher heat preservation temperature and heat preservation time, the atmosphere can ensure that the nano molybdenum oxide in the composite powder is fully reduced and is not oxidized for the second time, and simultaneously, the gas generated by the reaction is taken out of the furnace body.
The preparation method of the molybdenum-copper nano composite powder is characterized in that the heating and stirring temperature in the fifth step is more than 70 ℃; the copper salt is copper nitrate or copper chloride, the frequency of ultrasonic atomization is 1MHz to 2MHz, and the concentration of the copper salt in the superfine copper salt liquid drop is not less than 0.2g/mL; the bulk density of the copper-containing mixed powder is less than 1.5g/cm 3 . The invention can fully disperse and uniformly mix the copper salt and the molybdenum source by controlling the components, the concentration and the adding quality of the copper salt; the invention ensures that the copper salt is the nano-particles by controlling the ultrasonic atomization frequency, and is beneficial to generating the copper nano-particles in situ in the subsequent hydrogen reduction process.
The preparation method of the molybdenum-copper nano composite powder is characterized in that the segmented heat treatment process in the sixth step is as follows: heating to 500-650 ℃ at a heating rate of more than 1 ℃/min, then preserving heat for more than 1h, then heating to 750-950 ℃ at a heating rate of more than 1 ℃/min, and preserving heat for more than 1h, wherein the mass purity of hydrogen in the hydrogen atmosphere is more than 99%; the thickness of the copper-containing mixed powder in the segmented heat treatment is more than 5mm; the apparent density of the molybdenum-copper nano composite powder is less than 1g/cm 3 The porosity is more than 90 percent. The invention controls the sectional heatThe processing parameters are favorable for reducing the granularity of the nano composite powder and ensure that the molybdenum-copper nano composite powder with high dispersion and high porosity is obtained.
In addition, the invention also provides application of the molybdenum-copper nano composite powder prepared by the method in preparation of superfine nano molybdenum-copper composite materials.
Compared with the prior art, the invention has the following advantages:
1. the method comprises the steps of taking ammonium molybdate as a raw material, taking high-activity amorphous carbon nanoparticles as a nucleating agent and a pore-forming agent for decomposing the ammonium molybdate to prepare a composite precursor, then heating and decomposing the composite precursor to improve the nucleation rate of molybdenum trioxide and form steric hindrance, reduce the particle size of the molybdenum trioxide and improve the porosity, carrying out two-stage heating pre-reduction on a mixture of the molybdenum trioxide and the amorphous carbon nanoparticles as the precursor after ball milling and crushing, inheriting the appearance and the particle size of the molybdenum trioxide to obtain molybdenum dioxide and molybdenum composite powder, uniformly spraying superfine copper salt liquid drops into the pre-reduced powder, drying and stirring at ultrahigh speed to obtain nano copper-containing mixed powder, laying the nano copper-containing mixed powder and then carrying out hydrogen reduction, wherein in the reduction process, the copper salt nanoparticles are used as the nucleating agent to assist the nucleation of the molybdenum nanoparticles to further refine the particle size of the molybdenum powder, and simultaneously, the copper salt is converted into copper nanoparticles in situ to obtain the highly-dispersed and highly porous molybdenum-copper nano composite powder.
2. According to the method, ammonium molybdate is used as a raw material, and high-activity amorphous carbon nanoparticles with excellent dispersibility are used as a nucleating agent and a pore-forming agent for decomposing ammonium molybdate, so that the coalescence growth of molybdenum trioxide crystal nuclei is hindered, and the controllable preparation of the nano molybdenum trioxide with small granularity and loose structure is realized.
3. According to the invention, the nano copper salt liquid drops formed by ultrasonic atomization are sprayed into the nano precursor powder, so that the mixing uniformity is improved, and the particle size of the corresponding reduction product is refined by using the carbon nano particles and the copper salt nano particles.
4. According to the invention, copper salt is dissolved in ethanol and sprayed into heated pre-reduction powder, so that the rapid drying of copper salt liquid drops is realized, the in-situ granularity generation of copper oxide nanoparticles is further realized, and the molybdenum-copper nano composite powder with the average granularity of 30nm to 100nm is obtained through two-step reduction.
5. The invention has simple preparation process, low raw material cost and easy engineering application.
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 a composite precursor prepared in step one of example 1 of the present invention.
FIG. 2 is a low-magnification SEM image of the Mo-Cu nano composite powder prepared in example 1 of the present invention.
FIG. 3 is a high-magnification SEM image of the Mo-Cu nano composite powder prepared in example 1 of the present invention.
FIG. 4 is an EDS diagram of Mo in the Mo-Cu nanocomposite powder prepared in example 1 of the present invention.
FIG. 5 is an EDS diagram of Cu in the Mo-Cu nanocomposite powder prepared in example 1 of the present invention.
Detailed Description
Example 1
The embodiment comprises the following steps:
step one, adding 0.5g of amorphous carbon nano-particles, 10g of ammonium molybdate, 0.2g of surfactant and 0.2g of pore-forming agent into 100mL of deionized water, uniformly mixing, and then drying to obtain a composite precursor; the amorphous carbon nanoparticles have an average particle size of 20nm, wherein the mass content of carbon is greater than 98%; the mass purity of the ammonium molybdate is more than 99.7 percent; the surfactant is polyvinylpyrrolidone; the pore-forming agent is glucose; the drying is rotary evaporation, wherein the temperature of the rotary evaporation is 80 ℃, and the rotating speed is 200r/min;
step two, heating the composite precursor obtained in the step one to obtain a mixture of molybdenum trioxide and amorphous carbon nanoparticles; the heating treatment process comprises the following steps: heating to 500 ℃ at a heating rate of 10 ℃/min, and then preserving heat for 5h, wherein the atmosphere of the heating treatment is air;
step three, adding the mixture obtained in the step two into ethanol, then carrying out ball milling, and then sequentially carrying out drying and ultrahigh-speed stirring to obtain molybdenum trioxide and carbon composite powder; the adding amount of the ethanol is 66% of the mass of the mixture, the ball-material ratio in the ball milling is 2:1, the ball milling rotation speed is 200r/min, and the ball milling time is 6 hours; the rotating speed of the ultra-high speed stirring is 30000r/min, and the time is 200s;
step four, carrying out segmented heat treatment on the molybdenum trioxide and carbon composite powder obtained in the step three, and then carrying out ultrahigh-speed stirring to obtain molybdenum dioxide and molybdenum composite powder; the segmented heat treatment comprises the following steps: firstly heating to 850 ℃ at a heating rate of 30 ℃/min, then preserving heat for 3h, then heating to 1000 ℃ at a heating rate of 30 ℃/min, and then preserving heat for 3h, wherein the atmosphere of the segmented heat treatment is argon atmosphere; the thickness of the molybdenum trioxide and carbon composite powder in the segmented heat treatment is 10mm; the rotating speed of the ultra-high speed stirring is 30000r/min, and the time is 200s;
step five, heating and stirring the molybdenum dioxide and molybdenum composite powder obtained in the step four, then dropwise adding superfine copper salt liquid drops, drying and then carrying out ultrahigh-speed stirring to obtain copper-containing mixed powder; the preparation process of the superfine copper salt liquid drop comprises the following steps: dispersing copper salt into ethanol and carrying out ultrasonic atomization; the heating and stirring temperature is 70 ℃; the copper salt is copper nitrate, the ultrasonic atomization frequency is 1MHz, the particle size of the superfine copper salt liquid drop is less than 3 mu m, the concentration of the copper salt in the superfine copper salt liquid drop is 0.2g/mL, and 40mL of the superfine copper salt liquid drop is added into 100g of the molybdenum dioxide and molybdenum nano composite powder; the bulk density of the copper-containing mixed powder is less than 1.5g/cm 3 (ii) a The rotation speed of the ultra-high speed stirring is 10000r/min, and the time is 300s;
step six, carrying out segmented heat treatment on the copper-containing mixed powder obtained in the step five in a hydrogen atmosphere to obtain high-dispersion and high-porosity molybdenum-copper nano composite powder; the process of the segmented heat treatment comprises the following steps: heating to 500 ℃ at a heating rate of 5 ℃/min, then preserving heat for 2h, heating to 750 ℃ at a heating rate of 5 ℃/min, and then preserving heat for 3h, wherein the mass purity of hydrogen in the hydrogen atmosphere is more than 99%; the thickness of the copper-containing mixed powder in the staged heat treatment is 5mm.
Through detection, the loose package of the molybdenum-copper nano composite powder prepared in the embodiment is filledThe density is 0.8g/cm 3 The porosity was 92%.
Fig. 1 is an SEM image of the composite precursor prepared in step one of the present example, and it can be seen from fig. 1 that the composite powder has a fine particle size and a loose structure.
Fig. 2 is a low-power SEM image of the molybdenum-copper nanocomposite powder prepared in this example, fig. 3 is a high-power SEM image of the molybdenum-copper nanocomposite powder prepared in this example, fig. 4 is an EDS image of Mo in the molybdenum-copper nanocomposite powder prepared in this example, fig. 5 is an EDS image of Cu in the molybdenum-copper nanocomposite powder prepared in this example, and it can be seen from fig. 2 to fig. 5 that the particle size of the molybdenum-copper nanocomposite powder is further refined, the components are uniform, the average particle size is about 50nm, and the powder has a certain porosity, in which Mo and Cu are uniformly distributed.
Example 2
The embodiment comprises the following steps:
step one, adding 1.2g of amorphous carbon nano-particles, 20g of ammonium molybdate, 0.4g of surfactant and 0.4g of pore-forming agent into 100mL of deionized water, uniformly mixing, and then drying to obtain a composite precursor; the amorphous carbon nanoparticles have an average particle size of 40nm, wherein the mass content of carbon is greater than 98%; the mass purity of the ammonium molybdate is more than 99.7 percent; the surfactant is polyvinyl alcohol; the pore-forming agent is sucrose; the drying is spray drying, wherein the temperature of the spray drying is 120 ℃;
step two, heating the composite precursor obtained in the step one to obtain a mixture of molybdenum trioxide and amorphous carbon nanoparticles; the heating treatment process comprises the following steps: raising the temperature to 550 ℃ at a temperature raising rate of 30 ℃/min, and then preserving the heat for 4h, wherein the atmosphere of the heating treatment is oxygen;
step three, adding the mixture obtained in the step two into ethanol, then carrying out ball milling, and then sequentially carrying out drying and ultrahigh-speed stirring to obtain molybdenum trioxide and carbon composite powder; the adding amount of the ethanol is 80% of the mass of the mixture, the ball-to-material ratio in the ball milling is 3:1, the ball milling rotation speed is 250r/min, and the ball milling time is 6 hours; the rotating speed of the ultra-high speed stirring is 30000r/min, and the time is 200s;
step four, carrying out segmented heat treatment on the molybdenum trioxide and carbon composite powder obtained in the step three, and then carrying out ultrahigh-speed stirring to obtain molybdenum dioxide and molybdenum composite powder; the segmented heat treatment comprises the following steps: heating to 860 ℃ at a heating rate of 25 ℃/min, then preserving heat for 2.5h, then heating to 1020 ℃ at a heating rate of 20 ℃/min, and then preserving heat for 2.5h, wherein the atmosphere of the segmented heat treatment is argon atmosphere; the thickness of the molybdenum trioxide and carbon composite powder in the segmented heat treatment is 12mm; the rotating speed of the ultra-high speed stirring is 30000r/min, and the time is 200s;
step five, heating and stirring the molybdenum dioxide and molybdenum composite powder obtained in the step four, then dropwise adding superfine copper salt liquid drops, drying and then carrying out ultrahigh-speed stirring to obtain copper-containing mixed powder; the preparation process of the superfine copper salt liquid drop comprises the following steps: dispersing copper salt into ethanol and carrying out ultrasonic atomization; the heating and stirring temperature is 75 ℃; the copper salt is copper nitrate, the ultrasonic atomization frequency is 1MHz, the particle size of the superfine copper salt liquid drop is less than 3 mu m, the concentration of the copper salt in the superfine copper salt liquid drop is 0.3g/mL, and 20mL of the superfine copper salt liquid drop is added into 100g of the molybdenum dioxide and molybdenum nano composite powder; the bulk density of the copper-containing mixed powder is less than 1.5g/cm 3 (ii) a The rotating speed of the ultra-high speed stirring is 15000r/min, and the time is 300s;
step six, carrying out segmented heat treatment on the copper-containing mixed powder obtained in the step five in a hydrogen atmosphere to obtain high-dispersion and high-porosity molybdenum-copper nano composite powder; the process of the segmented heat treatment comprises the following steps: firstly heating to 530 ℃ at a heating rate of 4 ℃/min, then preserving heat for 2h, then heating to 800 ℃ at a heating rate of 4 ℃/min, and then preserving heat for 2h, wherein the mass purity of hydrogen in the hydrogen atmosphere is more than 99%; the thickness of the copper-containing mixed powder in the staged heat treatment is 10mm.
Through detection, the apparent density of the molybdenum-copper nano composite powder prepared in the embodiment is 0.9g/cm 3 The porosity was 91%.
Example 3
The embodiment comprises the following steps:
step one, adding 1.8g of amorphous carbon nano-particles, 30g of ammonium molybdate, 0.45g of surfactant and 0.75g of pore-forming agent into 100mL of deionized water, uniformly mixing, and then drying to obtain a composite precursor; the amorphous carbon nanoparticles have an average particle size of 60nm, wherein the mass content of carbon is greater than 98%; the mass purity of the ammonium molybdate is more than 99.7 percent; the surfactant is polyethylene glycol; the pore-forming agent is starch; the drying is spray drying, wherein the temperature of the spray drying is 240 ℃;
step two, heating the composite precursor obtained in the step one to obtain a mixture of molybdenum trioxide and amorphous carbon nanoparticles; the heating treatment process comprises the following steps: heating to 580 ℃ at a heating rate of 50 ℃/min, and then preserving heat for 3h, wherein the atmosphere of the heating treatment is air;
step three, adding the mixture obtained in the step two into ethanol, then carrying out ball milling, and then sequentially carrying out drying and ultrahigh-speed stirring to obtain molybdenum trioxide and carbon composite powder; the adding amount of the ethanol is 60% of the mass of the mixture, the ball-material ratio in the ball milling is 4:1, the ball milling rotating speed is 300r/min, and the ball milling time is 4 hours; the rotating speed of the ultra-high speed stirring is 30000r/min, and the time is 200s;
step four, carrying out segmented heat treatment on the molybdenum trioxide and carbon composite powder obtained in the step three, and then carrying out ultrahigh-speed stirring to obtain molybdenum dioxide and molybdenum composite powder; the segmented heat treatment comprises the following steps: heating to 870 ℃ at a heating rate of 20 ℃/min, then preserving heat for 2h, then heating to 1030 ℃ at a heating rate of 15 ℃/min, and then preserving heat for 2h, wherein the atmosphere of the segmented heat treatment is argon atmosphere; the thickness of the molybdenum trioxide and carbon composite powder in the segmented heat treatment is 15mm; the rotating speed of the ultra-high speed stirring is 30000r/min, and the time is 200s;
step five, heating and stirring the molybdenum dioxide and molybdenum composite powder obtained in the step four, then dropwise adding superfine copper salt liquid drops, drying and then carrying out ultrahigh-speed stirring to obtain copper-containing mixed powder; the preparation process of the superfine copper salt liquid drop comprises the following steps: dispersing copper salt into ethanol and carrying out ultrasonic atomization; the heating and stirring temperature is 80 ℃; the copper salt is copper chloride, the frequency of ultrasonic atomization is 1.5MHz, and the particle size of the superfine copper salt liquid drop is less than3 mu m, the concentration of copper salt in the superfine copper salt liquid drop is 0.4g/mL, and 30mL of superfine copper salt liquid drop is added into each 100g of the molybdenum dioxide and molybdenum nano composite powder; the bulk density of the copper-containing mixed powder is less than 1.5g/cm 3 (ii) a The rotation speed of the ultra-high speed stirring is 20000r/min, and the time is 250s;
step six, carrying out segmented heat treatment on the copper-containing mixed powder obtained in the step five in a hydrogen atmosphere to obtain high-dispersion and high-porosity molybdenum-copper nano composite powder; the process of the segmented heat treatment comprises the following steps: heating to 580 ℃ at a heating rate of 3 ℃/min, then preserving heat for 1.5h, heating to 850 ℃ at a heating rate of 3 ℃/min, and then preserving heat for 1.5h, wherein the mass purity of hydrogen in the hydrogen atmosphere is more than 99%; the thickness of the copper-containing mixed powder in the staged heat treatment is 10mm.
Through detection, the apparent density of the molybdenum-copper nano composite powder prepared in the embodiment is 0.9g/cm 3 The porosity was 92%.
Example 4
The embodiment comprises the following steps:
step one, adding 4g of amorphous carbon nano-particles, 40g of ammonium molybdate, 0.4g of surfactant and 1.0g of pore-forming agent into 100mL of deionized water, uniformly mixing, and then drying to obtain a composite precursor; the average particle size of the amorphous carbon nano particles is 80nm, wherein the mass content of carbon is more than 98%; the mass purity of the ammonium molybdate is more than 99.7 percent; the surfactant is polyvinyl alcohol and polyvinylpyrrolidone; the pore-forming agent is glucose; the drying is rotary evaporation, wherein the temperature of the rotary evaporation is 95 ℃, and the rotating speed is 500r/min;
step two, heating the composite precursor obtained in the step one to obtain a mixture of molybdenum trioxide and amorphous carbon nanoparticles; the heating treatment process comprises the following steps: heating to 600 ℃ at a heating rate of 80 ℃/min, and then preserving heat for 3h, wherein the atmosphere of the heating treatment is air;
step three, adding the mixture obtained in the step two into ethanol, then carrying out ball milling, and then sequentially carrying out drying and ultrahigh-speed stirring to obtain molybdenum trioxide and carbon composite powder; the adding amount of the ethanol is 70% of the mass of the mixture, the ball-to-material ratio in the ball milling is 5:1, the ball milling rotating speed is 350r/min, and the ball milling time is 3 hours; the rotating speed of the ultra-high speed stirring is 30000r/min, and the time is 200s;
step four, carrying out segmented heat treatment on the molybdenum trioxide and carbon composite powder obtained in the step three, and then carrying out ultrahigh-speed stirring to obtain molybdenum dioxide and molybdenum composite powder; the segmented heat treatment comprises the following steps: heating to 880 ℃ at a heating rate of 15 ℃/min, then preserving heat for 1.5h, then heating to 1040 ℃ at a heating rate of 10 ℃/min, and then preserving heat for 1.5h, wherein the atmosphere of the segmented heat treatment is argon atmosphere; the thickness of the molybdenum trioxide and carbon composite powder in the segmented heat treatment is 20mm; the rotating speed of the ultra-high speed stirring is 30000r/min, and the time is 200s;
step five, heating and stirring the molybdenum dioxide and molybdenum composite powder obtained in the step four, then dropwise adding superfine copper salt liquid drops, drying and then carrying out ultrahigh-speed stirring to obtain copper-containing mixed powder; the preparation process of the superfine copper salt liquid drop comprises the following steps: dispersing copper salt into ethanol and carrying out ultrasonic atomization; the heating and stirring temperature is 85 ℃; the copper salt is copper chloride, the ultrasonic atomization frequency is 2MHz, the particle size of the superfine copper salt liquid drop is less than 3 mu m, the concentration of the copper salt in the superfine copper salt liquid drop is 0.5g/mL, and 30mL of the superfine copper salt liquid drop is added into 100g of the molybdenum dioxide and molybdenum nano composite powder; the bulk density of the copper-containing mixed powder is less than 1.5g/cm 3 (ii) a The rotating speed of the ultra-high speed stirring is 25000r/min, and the time is 220s;
step six, carrying out segmented heat treatment on the copper-containing mixed powder obtained in the step five in a hydrogen atmosphere to obtain high-dispersion and high-porosity molybdenum-copper nano composite powder; the process of the segmented heat treatment comprises the following steps: heating to 620 ℃ at a heating rate of 2 ℃/min, then preserving heat for 1h, then heating to 900 ℃ at a heating rate of 2 ℃/min, and then preserving heat for 1h, wherein the mass purity of hydrogen in the hydrogen atmosphere is more than 99%; the thickness of the copper-containing mixed powder in the staged heat treatment is 15mm.
Through detection, the apparent density of the molybdenum-copper nano composite powder prepared in the embodiment is 0.9g/cm 3 The porosity was 93%.
Example 5
The embodiment comprises the following steps:
step one, adding 3.5g of amorphous carbon nano-particles, 50g of ammonium molybdate, 0.75g of surfactant and 1.5g of pore-forming agent into 100mL of deionized water, uniformly mixing, and then drying to obtain a composite precursor; the amorphous carbon nanoparticles have an average particle size of 100nm, wherein the mass content of carbon is greater than 98%; the mass purity of the ammonium molybdate is more than 99.7 percent; the surfactant is polyvinylpyrrolidone and polyethylene glycol; the pore-forming agent is glucose; the drying is rotary evaporation, wherein the temperature of the rotary evaporation is 100 ℃, and the rotating speed is 600r/min;
step two, heating the composite precursor obtained in the step one to obtain a mixture of molybdenum trioxide and amorphous carbon nanoparticles; the heating treatment process comprises the following steps: heating to 620 ℃ at a heating rate of 100 ℃/min, and then preserving heat for 2h, wherein the atmosphere of the heating treatment is air;
step three, adding the mixture obtained in the step two into ethanol, then carrying out ball milling, and then sequentially carrying out drying and ultrahigh-speed stirring to obtain molybdenum trioxide and carbon composite powder; the adding amount of the ethanol is 70% of the mass of the mixture, the ball-to-material ratio in the ball milling is 6:1, the ball milling rotating speed is 400r/min, and the ball milling time is 2h; the rotating speed of the ultra-high speed stirring is 30000r/min, and the time is 200s;
step four, carrying out segmented heat treatment on the molybdenum trioxide and carbon composite powder obtained in the step three, and then carrying out ultrahigh-speed stirring to obtain molybdenum dioxide and molybdenum composite powder; the segmented heat treatment comprises the following steps: heating to 900 ℃ at a heating rate of 10 ℃/min, then preserving heat for 1h, then heating to 1050 ℃ at a heating rate of 5 ℃/min, and then preserving heat for 1h, wherein the atmosphere of the segmented heat treatment is argon atmosphere; the thickness of the molybdenum trioxide and carbon composite powder in the segmented heat treatment is 25mm; the rotating speed of the ultra-high speed stirring is 30000r/min, and the time is 200s;
step five, heating and stirring the molybdenum dioxide and molybdenum composite powder obtained in the step four, then dropwise adding superfine copper salt liquid drops, drying and then carrying out ultrahigh-speed stirring to obtain the copper-containing composite powderMixing the powder; the preparation process of the superfine copper salt liquid drop comprises the following steps: dispersing copper salt into ethanol and carrying out ultrasonic atomization; the heating and stirring temperature is 90 ℃; the copper salt is copper nitrate, the ultrasonic atomization frequency is 2MHz, the particle size of the superfine copper salt liquid drop is less than 3 mu m, the concentration of the copper salt in the superfine copper salt liquid drop is 0.6g/mL, and 20mL of the superfine copper salt liquid drop is added into 100g of the molybdenum dioxide and molybdenum nano composite powder; the bulk density of the copper-containing mixed powder is less than 1.5g/cm 3 (ii) a The rotating speed of the ultra-high speed stirring is 30000r/min, and the time is 220s;
step six, carrying out segmented heat treatment on the copper-containing mixed powder obtained in the step five in a hydrogen atmosphere to obtain high-dispersion and high-porosity molybdenum-copper nano composite powder; the process of the segmented heat treatment comprises the following steps: firstly heating to 650 ℃ at a heating rate of 1 ℃/min, then preserving heat for 1h, then heating to 950 ℃ at a heating rate of 1 ℃/min, and then preserving heat for 1h, wherein the mass purity of hydrogen in the hydrogen atmosphere is more than 99%; the thickness of the copper-containing mixed powder in the staged heat treatment is 20mm.
Through detection, the apparent density of the molybdenum-copper nano composite powder prepared in the embodiment is 0.9g/cm 3 The porosity was 93%.
The above description is only a 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 (10)
1. The preparation method of the molybdenum-copper nano composite powder is characterized by comprising the following steps of:
adding amorphous carbon nano-particles, ammonium molybdate, a surfactant and a pore-forming agent into deionized water, uniformly mixing, and drying to obtain a composite precursor; the addition amount of the amorphous carbon nano particles is 5% -10% of the mass of ammonium molybdate;
step two, heating the composite precursor obtained in the step one to obtain a mixture of molybdenum trioxide and amorphous carbon nanoparticles;
step three, adding the mixture obtained in the step two into ethanol, then carrying out ball milling, and then sequentially carrying out drying and ultrahigh-speed stirring to obtain molybdenum trioxide and carbon composite powder;
step four, carrying out segmented heat treatment on the molybdenum trioxide and carbon composite powder obtained in the step three, and then carrying out ultrahigh-speed stirring to obtain molybdenum dioxide and molybdenum composite powder; the segmented heat treatment comprises the following steps: firstly heating to 800-950 ℃, then preserving heat for more than 1h, then heating to 1000-1100 ℃, and preserving heat for more than 1 h;
step five, heating and stirring the molybdenum dioxide and molybdenum composite powder obtained in the step four, then dropwise adding superfine copper salt liquid drops, drying and then carrying out ultrahigh-speed stirring to obtain copper-containing mixed powder; the preparation process of the superfine copper salt liquid drop comprises the following steps: dispersing copper salt into ethanol and carrying out ultrasonic atomization;
and step six, carrying out sectional heat treatment on the copper-containing mixed powder obtained in the step five in a hydrogen atmosphere to obtain the molybdenum-copper nano composite powder with high dispersion and high porosity.
2. The method for preparing molybdenum-copper nano composite powder according to claim 1, wherein in the first step, the average particle size of the amorphous carbon nano particles is from 20nm to 100nm, and the mass content of carbon is more than 98%; the mass purity of the ammonium molybdate is more than 99.7 percent; the mass ratio of ammonium molybdate to water in the composite precursor is 0.1 to 0.5:1; the surfactant is one or more of polyvinyl alcohol, polyvinylpyrrolidone and polyethylene glycol, and the addition amount of the surfactant is 1-2% of the mass of ammonium molybdate; the pore-forming agent is glucose, sucrose or starch, and the addition amount of the pore-forming agent is 2-3% of the mass of ammonium molybdate.
3. The method for preparing molybdenum-copper nano composite powder according to claim 1, wherein the drying in the first step is rotary evaporation, the temperature of the rotary evaporation is not less than 50 ℃, and the rotating speed is not less than 200r/min.
4. The method for preparing molybdenum-copper nano composite powder according to claim 1, wherein the heating treatment in the second step comprises the following steps: raising the temperature to 500-650 ℃ at a temperature raising rate of not less than 10 ℃/min, and then preserving the temperature for more than 2h, wherein the atmosphere of the heating treatment is air or oxygen.
5. The method for preparing molybdenum-copper nano composite powder according to claim 1, wherein the addition amount of ethanol in the third step is 60-80% of the mass of the mixture, the ball-to-material ratio in ball milling is not less than 2:1, the ball milling rotation speed is not less than 200r/min, and the ball milling time is not less than 2h.
6. The method for preparing molybdenum-copper nano composite powder according to claim 1, wherein the rotation speed of the ultra-high speed stirring in the third step, the fourth step and the fifth step is more than 10000r/min, and the time is more than 200s.
7. The method for preparing molybdenum-copper nano composite powder according to claim 1, wherein the atmosphere of the step four is argon atmosphere; the thickness of the molybdenum trioxide and carbon composite powder in the segmented heat treatment is not less than 10mm.
8. The method for preparing molybdenum-copper nano composite powder according to claim 1, wherein the temperature of heating and stirring in the fifth step is more than 70 ℃; the copper salt is copper nitrate or copper chloride, the frequency of ultrasonic atomization is 1 MHz-2MHz, and the concentration of the copper salt in the superfine copper salt liquid drop is not less than 0.2g/mL; the bulk density of the copper-containing mixed powder is less than 1.5g/cm 3 。
9. The method for preparing molybdenum-copper nano composite powder according to claim 1, wherein the step six of the step of the segmented heat treatment comprises the following steps: heating to 500-650 ℃ at a heating rate of more than 1 ℃/min, then preserving heat for more than 1h, then heating to 750-950 ℃ at a heating rate of more than 1 ℃/min, and then preserving heat for more than 1hThe mass purity of the hydrogen in the hydrogen atmosphere is more than 99 percent; the thickness of the copper-containing mixed powder in the segmented heat treatment is more than 5mm; the apparent density of the molybdenum-copper nano composite powder is less than 1g/cm 3 The porosity is greater than 90%.
10. The application of the molybdenum-copper nano composite powder prepared by the method as claimed in any one of claims 1 to 9, which is characterized in that the nano composite powder is used for preparing a nano molybdenum-copper composite material.
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