CN108339989B - Simple preparation method of nano-grade tungsten-copper precursor powder - Google Patents
Simple preparation method of nano-grade tungsten-copper precursor powder Download PDFInfo
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Abstract
A simple preparation method of nano-scale tungsten-copper precursor powder comprises the steps of preparing corresponding solution by using sodium tungstate dihydrate and copper nitrate trihydrate as raw materials, dripping sodium tungstate solution into copper nitrate solution containing copper complex ions at the speed of 1-10 drops/s, adjusting the pH value of the mixed solution by using ammonia water or nitric acid, and directly putting the mixed solution into a vacuum drying oven for thermochemical reaction to prepare the nano-scale tungsten-copper precursor powder. The method can be used for preparing the tungsten-copper precursor powder with uniform mixing, fine particles and high purity, and compared with a hydrothermal method, the method has the remarkable characteristics of short production period, no need of a reaction kettle and low preparation cost.
Description
Technical Field
The invention relates to the field of powder preparation in the powder metallurgy technology, in particular to a simple preparation method of nano-grade tungsten-copper precursor powder.
Background
The tungsten-copper composite material prepared by the powder metallurgy method is developing and optimizing in the direction of high compactness and high performance, and the quality of a powder metallurgy product has a great relationship with the performance of powder. Therefore, the preparation of the compact tungsten-copper composite material puts higher technical requirements on the synthesis, preparation and forming processes of the powder. Because the intersolubility of tungsten and copper is poor, a completely compact tungsten-copper composite material is not easy to obtain. Research results show that the densification process of the material with higher tungsten content is more dependent on the particle size of the powder, so that the preparation of the fine-grain high-density tungsten-copper composite material by adopting the tungsten-copper fine powder or the superfine powder becomes one of the development trends, and the key problem is the preparation of the superfine tungsten-copper composite powder.
At present, the preparation method of the superfine tungsten-copper composite powder is mainly divided into a physical method and a chemical method. Although the physical method has the characteristics of simple operation, low cost and the like, impurities are easily introduced in the preparation process, so that the performance of the tungsten-copper composite material is influenced. The hydrothermal method is an important method for preparing the nano material by a chemical method, and the prepared powder can completely realize the control of the size and the shape of crystal grains by controlling the temperature and the time, and has high particle purity, good dispersibility, good crystal form and controllability. However, when the hydrothermal method is used for preparing the superfine tungsten-copper composite powder, the production period is longer, the required energy consumption is higher, and the requirements of energy conservation and emission reduction advocated at present are not met.
Therefore, the invention provides a simple preparation method according to the defects of a hydrothermal method, and the literature investigation results show that the simple preparation method of the nano-scale tungsten-copper precursor powder has no related reports.
Disclosure of Invention
The invention aims to solve the problems of long production period and high energy consumption in the existing hydrothermal method powder preparation technology, and provides a simple preparation method of nano-grade tungsten-copper precursor powder.
In order to achieve the purpose and solve the problems in the prior art, the invention adopts the technical scheme that:
a simple preparation method of nano-grade tungsten-copper precursor powder comprises the steps of solution preparation, solution mixing reaction and product treatment;
in the preparation of the solution, weighing raw materials according to the mass percentage of tungsten and copper in the target composite powder, preparing a sodium tungstate solution and a copper nitrate solution, then adding ammonia water into the copper nitrate solution, and fully mixing at 30 ℃ to generate sufficient copper complex ions in the solution;
in the step of solution mixing reaction, dripping the obtained sodium tungstate solution into a copper nitrate solution containing copper complex ions at a speed of 1-10 drops/s, then adjusting the pH value of the mixed solution to 4.0-6.2, fully stirring the mixed solution in a magnetic stirrer at a speed of 60r/min for 2-5 hours, then placing the stirred mixed solution in a vacuum degree of 100pa, reacting the mixed solution at a temperature of 100-150 ℃ for 1-2 hours, and cooling the mixed solution to room temperature for later use;
and filtering and washing the cooled reaction product, and freeze-drying to obtain the nano-grade tungsten-copper precursor powder.
When the solution is prepared, the raw materials for preparing the sodium tungstate solution and the copper nitrate solution are sodium tungstate dihydrate and copper nitrate trihydrate respectively, and the concentration of the prepared sodium tungstate solution and the prepared copper nitrate solution is 0.2-0.8 mol/L.
In the treatment process of the product, the reaction product is cleaned by deionized water and absolute ethyl alcohol through ultrasonic cleaning.
After the mixed solution is obtained, adjusting the pH value of the mixed solution by using ammonia water or nitric acid, wherein the volume concentration of the ammonia water or nitric acid is 10-35%.
When ammonia water is added into the copper nitrate solution, the ammonia water is excessive by 3-10%.
When the raw materials are weighed to prepare the solution, the sodium tungstate dihydrate and the copper nitrate trihydrate are weighed according to the mass percent of 50-93% of W and 7-50% of Cu in the target composite powder.
Compared with a hydrothermal method adopted in the prior art, the simple preparation method of the nano-scale tungsten-copper precursor powder has the beneficial effects that:
according to the invention, the mixed solution is subjected to chemical reaction under the low-temperature vacuum condition, and the reported hydrothermal reaction process with high pressure and high heat for a long time in the preparation of the tungsten-copper precursor powder by a hydrothermal method is optimized, so that the production period for preparing the nano tungsten-copper precursor powder is shortened by 10-30 h, and the energy consumption is reduced.
Compared with the tungsten-copper precursor powder prepared by a hydrothermal method, the method controls the speed of dripping the sodium tungstate solution into the mixed solution of copper nitrate and ammonia water with excessive copper complex ions so as to control the precipitation speed of tungsten and copper atoms, so that the nano-scale tungsten-copper precursor powder can be obtained under the low-temperature vacuum condition, and the prepared tungsten-copper precursor powder can obtain superfine WCu composite powder with uniform components through subsequent hydrogen reduction, thereby enabling the preparation of high-performance tungsten-copper composite materials to be possible.
Drawings
FIG. 1 is an XRD diffraction pattern of the precursor powder of tungsten and copper prepared by the invention;
FIG. 2 is an SEM image of a W-Cu precursor powder prepared by the present invention;
FIG. 3 is an XRD diffractogram of WCu composite powder obtained by reducing tungsten copper precursor powder particles in accordance with the present invention;
FIG. 4 is an SEM image of WCu composite powder obtained by reducing tungsten copper precursor powder particles according to the present invention;
FIG. 5 is a view showing the distribution of W element in the WCu composite powder in the visual field shown in FIG. 4;
fig. 6 shows the distribution of Cu elements in the WCu composite powder in the visual field shown in fig. 4.
Detailed Description
The technical scheme of the simple preparation method of the nano-scale tungsten-copper precursor powder of the present invention is further described below by specific embodiments.
Example 1
A simple preparation method of nano-grade tungsten-copper precursor powder comprises the following steps:
weighing sodium tungstate dihydrate and copper nitrate trihydrate according to the mass percent of 50-60% and 40-50% of Cu in the target composite powder, and respectively preparing the sodium tungstate dihydrate and the copper nitrate trihydrate into solutions with the concentration of 0.8 mol/L;
adding excessive ammonia water into the obtained copper nitrate trihydrate solution, and fully mixing the excessive ammonia water at the temperature of 30 ℃ to generate sufficient copper complex ions in the solution, wherein the ammonia water can be excessive by 3-5% when being added;
thirdly, dripping a sodium tungstate solution into the solution obtained in the second step at the speed of 1-3 drops/s, then adding ammonia water or nitric acid to adjust the pH value of the mixed solution to 4.0-6.2, and fully stirring for 5 hours in a magnetic stirrer at the speed of 60 r/min;
step four, putting the mixed solution obtained in the step three into a constant-temperature vacuum drying oven, reacting for 1 hour at the vacuum degree of 100pa and the temperature of 100 ℃, and cooling to room temperature in the oven;
and step five, filtering the product obtained in the step four, then ultrasonically cleaning the product by using deionized water and absolute ethyl alcohol, and then freeze-drying the product to obtain a finished product.
The volume concentration of ammonia water and nitric acid used in the preparation process is 10-35%.
Example 2
A simple preparation method of nano-grade tungsten-copper precursor powder comprises the following steps:
weighing sodium tungstate dihydrate and copper nitrate trihydrate according to the mass percent of 60-70% and 30-40% of Cu in the target composite powder, and respectively preparing the sodium tungstate dihydrate and the copper nitrate trihydrate into solutions with the concentration of 0.6 mol/L;
adding excessive ammonia water into the obtained copper nitrate trihydrate solution, and fully mixing the excessive ammonia water at the temperature of 30 ℃ to generate sufficient copper complex ions in the solution, wherein the excessive ammonia water is 5-8% during addition;
thirdly, dropwise adding a sodium tungstate solution into the solution obtained in the second step at the speed of 3-5 drops/s, then adding ammonia water or nitric acid to adjust the pH value of the mixed solution to 4.0-6.2, and fully stirring for 4 hours in a magnetic stirrer at the speed of 60 r/min;
step four, putting the mixed solution obtained in the step three into a constant-temperature vacuum drying oven, reacting for 2 hours at the vacuum degree of 100pa and the temperature of 100 ℃, and cooling to room temperature in the oven;
and step five, filtering the product obtained in the step four, then ultrasonically cleaning the product by using deionized water and absolute ethyl alcohol, and then freeze-drying the product to obtain a finished product.
The volume concentration of ammonia water and nitric acid used in the preparation process is 10-35%.
Example 3
A simple preparation method of nano-grade tungsten-copper precursor powder comprises the following steps:
weighing sodium tungstate dihydrate and copper nitrate trihydrate according to the mass percent of 70-80% and 20-30% of the W and the mass percent of the Cu in the target composite powder, and respectively preparing the sodium tungstate dihydrate and the copper nitrate trihydrate into solutions with the concentration of 0.4 mol/L;
adding excessive ammonia water into the obtained copper nitrate trihydrate solution, and fully mixing the excessive ammonia water at the temperature of 30 ℃ to generate sufficient copper complex ions in the solution, wherein the excessive ammonia water is 8-10% during addition;
thirdly, dripping a sodium tungstate solution into the solution obtained in the second step at a speed of 5-8 drops/s, then adding ammonia water or nitric acid to adjust the pH value of the mixed solution to 4.0-6.2, and fully stirring for 3 hours in a magnetic stirrer at a speed of 60 r/min;
step four, putting the mixed solution obtained in the step three into a constant-temperature vacuum drying oven, reacting for 1 hour at the vacuum degree of 100pa and the temperature of 150 ℃, and cooling to room temperature in the oven;
fifthly, filtering the product obtained in the fourth step, then ultrasonically cleaning the product by using deionized water and absolute ethyl alcohol, and then freeze-drying the product to obtain a finished product;
the volume concentration of ammonia water and nitric acid used in the preparation process is 10-35%.
Example 4
A simple preparation method of nano-grade tungsten-copper precursor powder comprises the following steps:
weighing sodium tungstate dihydrate and copper nitrate trihydrate according to the mass percent of 80-93% and 7-20% of Cu in the target composite powder, and respectively preparing the sodium tungstate dihydrate and the copper nitrate trihydrate into solutions with the concentration of 0.2 mol/L;
adding excessive ammonia water into the obtained copper nitrate trihydrate solution, and fully mixing the excessive ammonia water at the temperature of 30 ℃ to generate sufficient copper complex ions in the solution, wherein the excessive ammonia water is 3-10% during addition;
thirdly, dripping a sodium tungstate solution into the solution obtained in the second step at the speed of 8-10 drops/s, then adding ammonia water or nitric acid to adjust the pH value of the mixed solution to 4.0-6.2, and fully stirring for 2 hours in a magnetic stirrer at the speed of 60 r/min;
step four, putting the mixed solution obtained in the step three into a constant-temperature vacuum drying oven, reacting for 2 hours at the vacuum degree of 100pa and the temperature of 150 ℃, and cooling to room temperature in the oven;
and step five, filtering the product obtained in the step four, then ultrasonically cleaning the product by using deionized water and absolute ethyl alcohol, and then freeze-drying the product to obtain a finished product.
The volume concentration of ammonia water and nitric acid used in the preparation process is 10-35%.
As shown in FIG. 1, the XRD diffraction pattern of the tungsten-copper precursor powder nanoparticles prepared by the present invention is a tungsten-copper oxide mixed powder.
As shown in FIG. 2, SEM image of the tungsten-copper precursor powder prepared by the present invention shows that the tungsten-copper precursor powder prepared by the present invention has uniform nanoparticles.
As shown in FIG. 3, the purity of the WCu composite powder obtained by hydrogen reduction of the tungsten-copper precursor powder of the present invention is high.
As shown in FIG. 4, the SEM image of the WCu composite powder obtained by hydrogen reduction of the tungsten-copper precursor powder of the invention shows that the WCu composite powder prepared by the invention has fine particles and uniform component distribution.
The invention is not described in part in the prior art.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (5)
1. A simple preparation method of nano-grade tungsten-copper precursor powder comprises the steps of solution preparation, solution mixing reaction and product treatment; in the preparation of the solution, weighing raw materials according to the mass percent of 50-93% of W and 7-50% of Cu in the target composite powder, preparing a sodium tungstate solution and a copper nitrate solution, then adding ammonia water with the excess of 3-10% into the copper nitrate solution, and fully mixing at 30 ℃ to generate sufficient copper complex ions in the solution; the method is characterized in that: in the step of solution mixing reaction, dripping the obtained sodium tungstate solution into a copper nitrate solution containing copper complex ions at a speed of 1-10 drops/s, then adjusting the pH value of the mixed solution to 4.0-6.2, fully stirring the mixed solution in a magnetic stirrer at a speed of 60r/min for 2-5 hours, then placing the stirred mixed solution in a vacuum degree of 100pa, reacting the mixed solution at a temperature of 100-150 ℃ for 1-2 hours, and cooling the mixed solution to room temperature for later use;
and filtering and washing the cooled reaction product, and freeze-drying to obtain the nano-grade tungsten-copper precursor powder.
2. The simple preparation method of the nano-scale tungsten-copper precursor powder according to claim 1, which is characterized by comprising the following steps: the raw materials for preparing the sodium tungstate solution and the copper nitrate solution are sodium tungstate dihydrate and copper nitrate trihydrate respectively, and the concentration of the prepared sodium tungstate solution and the prepared copper nitrate solution is 0.2-0.8 mol/L.
3. The simple preparation method of the nano-scale tungsten-copper precursor powder according to claim 1, which is characterized by comprising the following steps: the cleaning of the reaction product is ultrasonic cleaning by deionized water and absolute ethyl alcohol.
4. The simple preparation method of the nano-scale tungsten-copper precursor powder according to claim 1, which is characterized by comprising the following steps: and adjusting the pH of the mixed solution by using ammonia water or nitric acid.
5. The simple preparation method of the nano-scale tungsten-copper precursor powder according to claim 4, which is characterized by comprising the following steps: the volume concentration of the ammonia water or the nitric acid is 10-35 percent.
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