CN114101663B - Spherical nickel powder and preparation method and application thereof - Google Patents
Spherical nickel powder and preparation method and application thereof Download PDFInfo
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- CN114101663B CN114101663B CN202210098857.6A CN202210098857A CN114101663B CN 114101663 B CN114101663 B CN 114101663B CN 202210098857 A CN202210098857 A CN 202210098857A CN 114101663 B CN114101663 B CN 114101663B
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Abstract
The invention provides spherical nickel powder and a preparation method and application thereof, wherein the method comprises the following steps: adding the graded nickel powder to be treated into a solution system containing a cationic surfactant, and cleaning to obtain modified nickel powder; adding the modified nickel powder into the graphene oxide dispersion liquid to obtain modified nickel powder coated by graphene oxide; and spheroidizing the modified nickel powder coated by the graphene oxide by using plasma spheroidizing equipment to obtain the spherical nickel powder. According to the invention, the modification of the nickel powder by the graphene oxide is realized through the electrostatic adsorption effect, the universality of the plasma spheroidizing equipment is high, and the introduction of the graphene oxide effectively makes up the problem of poor high-temperature thermal conductivity of the nickel powder, so that the spheroidizing degree and uniformity of the nickel powder are improved.
Description
Technical Field
The invention relates to the technical field of metal powder materials, in particular to spherical nickel powder and a preparation method and application thereof.
Background
The 3D printing process is a novel printing technology, the metal powder is the most important ring in the 3D printing process, the product printed by the spherical metal powder has the advantages of surface gloss, small shrinkage rate, difficult deformation and stable mechanical property, and compared with the traditional metal powder, the performance of the product is greatly improved.
The metal powder adopted in the 3D printing process needs to have good plasticity and also needs to meet the requirements of high powder spheroidization rate, good sphericity, high uniformity and the like. The nickel powder is a metal powder commonly used in the 3D printing process, however, due to low high-temperature mobility and poor high-temperature thermal conductivity of nickel, the spheroidization degree of the nickel powder after plasma spheroidization is limited, the sphericity and the uniformity are not high, and the application of the nickel powder in the fields of 3D printing and injection molding is greatly limited.
Therefore, how to improve the spheroidization rate, the sphericity and the uniformity of the nickel powder is a problem which needs to be solved at present.
It is noted that this section is intended to provide a background or context to the embodiments of the disclosure that are recited in the claims. The description herein is not admitted to be prior art by inclusion in this section.
Disclosure of Invention
The embodiment of the invention provides spherical nickel powder and a preparation method and application thereof, aiming at solving the problems of limited spheroidization degree, low sphericity and low uniformity of the nickel powder in the prior art.
In a first aspect, an embodiment of the present invention provides a method for preparing spherical nickel powder, including:
adding the graded nickel powder to be treated into a solution system containing a cationic surfactant, and cleaning to obtain modified nickel powder;
adding the modified nickel powder into the graphene oxide dispersion liquid to obtain modified nickel powder coated by graphene oxide;
and spheroidizing the modified nickel powder coated by the graphene oxide by using plasma spheroidizing equipment to obtain the spherical nickel powder.
In a preferred embodiment of the first aspect of the present invention, in the step of obtaining the modified nickel powder, the nickel powder is one or more selected from the group consisting of electrolytic nickel powder, carbonyl nickel powder, reduced nickel powder, and atomized nickel powder.
In a preferred mode of the first aspect of the present invention, in the step of obtaining the modified nickel powder, the cationic surfactant is one or more selected from a silane coupling agent, melamine, cetyltrimethylammonium bromide, and octadecyltrimethylammonium chloride.
In a preferred embodiment of the first aspect of the present invention, in the step of obtaining the modified nickel powder, the mass ratio of the cationic surfactant to the nickel powder is 1 to 3:10 to 40.
In a preferred embodiment of the first aspect of the present invention, in the step of obtaining the modified nickel powder, the cationic surfactant is added to ethanol or water and stirred for 5 to 20min when preparing the solution system containing the cationic surfactant.
In a preferred mode of the first aspect of the present invention, in the step of obtaining the modified nickel powder, the graded nickel powder to be treated is added into a solution system containing a cationic surfactant at 25 to 65 ℃, stirred for 10 to 30min, and washed with an ethanol solution.
In a preferred embodiment of the first aspect of the present invention, in the step of obtaining modified nickel powder coated with graphene oxide, the mass ratio of the graphene oxide to the modified nickel powder is 2 to 5: 1000.
In a preferred aspect of the first aspect of the present invention, in the step of obtaining the spherical nickel powder, the plasma spheroidizing apparatus has an oscillation frequency of 4MHz, a plasma anode power of 20 to 26KW, a powder feeding amount of 16 to 54g/min, and a carrier gas of H2Or N2The air supply amount is 0.3 to 0.4m3H, Ar as a side gas and 5.0m of gas delivery3The central gas is Ar, the gas supply amount is 1.0-1.5 m3/h。
In a second aspect, embodiments of the present invention provide spherical nickel powder produced by the method for producing spherical nickel powder according to any one of the first aspect and the preferred embodiments thereof.
In the third invention, the embodiment of the present invention also provides an application of the spherical nickel powder prepared by the method for preparing spherical nickel powder described in any one of the first aspect and the preferred embodiment thereof in a 3D printing process.
The spherical nickel powder and the preparation method and the application thereof provided by the embodiment of the invention are characterized in that the graded nickel powder to be treated is added into a solution system containing a cationic surfactant for modification to obtain the modified nickel powder; adding the modified nickel powder into the graphene oxide dispersion liquid, so that graphene oxide is attached to the surface of the modified nickel powder, and obtaining modified nickel powder coated by graphene oxide; and finally, spheroidizing the modified nickel powder coated by the graphene oxide by using plasma spheroidizing equipment to obtain the spherical nickel powder with high uniformity and high spheroidization degree.
According to the invention, the modification of the nickel powder by the graphene oxide is realized through the electrostatic adsorption effect, the problem of poor high-temperature heat conductivity of the nickel powder can be effectively solved by the adhesion of the graphene on the surface layer of the graphene, the universality of plasma spheroidizing equipment is high, the intrinsic heat conductivity of the graphene oxide is recovered by high-temperature reduction of the graphene oxide in the subsequent plasma spheroidizing, the condition of insufficient high-temperature heat conductivity of the nickel is compensated by the heat conduction effect of the high-temperature reduced graphene oxide, and the spheroidizing degree of the nickel powder can be effectively increased. Meanwhile, the large surface binding energy difference between the high-temperature reduction graphene oxide and the nickel ensures that the interface acting force is extremely weak, the whole process avoids the introduction of impurities in the nickel base, ensures the purity of the nickel powder after spheroidization, can also block the deposition growth of nickel molten drops, refines the granularity of the nickel powder after spheroidization, and ensures the uniformity.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a flow chart illustrating a method for preparing spherical nickel powder according to an embodiment of the present invention;
fig. 2 is a scanning electron microscope image of spherical nickel powder prepared by the method for preparing spherical nickel powder according to the embodiment of the present invention.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that: like reference numbers and letters refer to like items in the following figures, and thus, once an item is defined in one figure, it need not be further defined and explained in subsequent figures.
The nickel powder is used as a metal powder commonly used in a 3D printing process, and due to the poor high-temperature thermal conductivity of the nickel powder, the sphericity of the spheroidized nickel powder is limited, and the sphericity and the uniformity are not high, so that the application of the nickel powder in the fields of 3D printing and injection molding is limited to a great extent.
Based on this, referring to fig. 1, an embodiment of the present invention discloses a method for preparing spherical nickel powder, which mainly includes the following steps:
101. and adding the graded nickel powder to be treated into a solution system containing a cationic surfactant, and cleaning to obtain the modified nickel powder.
In this step, nickel is subjected to preliminary modification because nickel has a limited sphericity due to its poor high-temperature thermal conductivity, thereby greatly affecting its subsequent applications.
The graded nickel powder to be treated is added into a solution system containing a cationic surfactant, and the modified nickel powder can be obtained after cleaning, so that the modification of the nickel powder by the graphene oxide can be realized through the electrostatic adsorption effect subsequently.
The graded nickel powder refers to nickel powder subjected to air flow grading treatment. After air flow classification, the particle size distribution of the nickel powder becomes narrow, and preparation can be made for subsequent spheroidizing treatment.
Preferably, in this step 101, the nickel powder is selected from one or more of electrolytic nickel powder, carbonyl nickel powder, reduced nickel powder, and atomized nickel powder.
Specifically, the nickel powder to be treated is preferably one or more selected from electrolytic nickel powder, carbonyl nickel powder, reduced nickel powder and atomized nickel powder.
The selected nickel powders are flaky, spheroidal or dendritic nickel powders, the morphology of which depends on the specific preparation method, but the nickel powders are not spherical. The nickel powder selected in the embodiment of the invention basically comprises all nickel powder types, so that the spheroidizing method of the nickel powder in the embodiment of the invention has wide universality, and is not only a single treatment method for certain type of nickel powder.
Preferably, in the step 101, the cationic surfactant is selected from one or more of silane coupling agent, melamine, cetyl trimethyl ammonium bromide and stearyl trimethyl ammonium chloride.
Specifically, the cationic surfactant is preferably one or more selected from silane coupling agent, melamine, cetyl trimethyl ammonium bromide and octadecyl trimethyl ammonium chloride.
The cationic surfactant is selected to provide cationic groups, so that the surface of the nickel powder can be positively charged, and good electrostatic adsorption with graphene oxide can be realized subsequently. Of course, other similar cationic surfactants can be selected by those skilled in the art in addition to the preferred concentrated cationic surfactants described above.
Preferably, in the step 101, the mass ratio of the cationic surfactant to the nickel powder is 1-3: 10-40.
Specifically, the mass ratio of the cationic surfactant to the nickel powder is preferably 1-3: 10-40 according to the difference of the repeated sizes of the hydrolytic groups of different cationic surfactants. At this mass ratio, it is possible to ensure that the nickel powder is sufficiently modified.
Preferably, in the step 101, when the solution system containing the cationic surfactant is prepared, the cationic surfactant is added into ethanol or water and stirred for 5-20 min.
Specifically, when a solution system containing the cationic surfactant is prepared, the cationic surfactant is added into ethanol or water and stirred for 5-20 min.
Due to the fact that the solubility of different cationic surfactants in a solvent is different, in order to ensure good dissolving and hydrolyzing effects, the stirring time is determined according to the dissolving time required by the different cationic surfactants, and preferably is stirred for 5-20 min, so that the good dissolving and hydrolyzing effects can be achieved. .
Preferably, in the step 101, the graded nickel powder to be treated is added into a solution system containing a cationic surfactant at 25-65 ℃, stirred for 10-30 min, and washed by an ethanol solution.
Specifically, when modifying the nickel powder, adding the graded nickel powder to be treated into a solution system containing a cationic surfactant at 25-65 ℃, and stirring for 10-30 min.
Because different cationic surfactants are mixed with the nickel powder, the modification degree of the nickel powder can be different under different stirring time, and in addition, the activity of the cationic surfactant can be improved by increasing the temperature, so that the modification speed is accelerated, but the temperature cannot be too high. Therefore, through analysis and repeated tests, the modification degree of the nickel powder is relatively complete when the modification temperature is 25-65 ℃ and the stirring time is 10-30 min.
After the modification is finished, the residual excessive cationic surfactant on the surface of the modified nickel powder can be removed by cleaning with an ethanol solution.
102. And adding the modified nickel powder into the graphene oxide dispersion liquid to obtain the modified nickel powder coated by the graphene oxide.
In the step, the modified nickel powder obtained in the step after the preliminary modification is added into graphene oxide dispersion liquid, the modification of the nickel powder by graphene oxide is further realized under the action of electrostatic adsorption, so that the graphene oxide is attached to the surface layer of the nickel powder, and the modified nickel powder coated by the graphene oxide is obtained.
The graphene oxide is attached to the surface layer of the nickel powder, so that the problem of poor high-temperature heat conductivity of the nickel powder can be effectively solved, the spheroidization degree of the nickel powder can be improved, the finally prepared nickel powder has good sphericity and high uniformity, and the requirement of a 3D printing process can be met.
Preferably, in the step 102, the mass ratio of the graphene oxide to the modified nickel powder is 2-5: 1000.
Specifically, the mass ratio of the graphene oxide to the modified nickel powder is preferably 2-5: 1000.
The graphene oxide is introduced not for the purpose of performing a nano-reinforcing and toughening effect on nickel powder or a subsequent nickel-based material, but for the purpose of performing a good heat transfer effect. Plasma spheroidization is an instant heat transfer effect, and the dispersion degree of the graphene oxide can be ensured by the content of the graphene oxide in a thousandth ratio, so that the agglomeration phenomenon is avoided.
Meanwhile, the graphene oxide on the surface of the modified nickel powder is ensured to be few-layer graphene oxide, the thermal conductivity of the graphene is ensured, and the optimal spheroidizing heat transfer effect is realized under the condition of the minimum addition amount. A small amount of graphene oxide is reduced into graphene due to high-temperature thermal expansion after the spheroidizing process, and the surface active groups volatilize at the moment so that the graphene oxide has no binding force with nickel powder and is separated with carrier gas flow after instantaneous heat transfer. In addition, due to light weight, graphene can be conveyed to a gas collecting and filtering system along with carrier gas, and cannot be mixed into spheroidized nickel powder, so that the introduction of impurities in nickel base is avoided.
103. And spheroidizing the modified nickel powder coated by the graphene oxide by using plasma spheroidizing equipment to obtain the spherical nickel powder.
In the step, the modified nickel powder coated by the graphene oxide obtained in the step is added into plasma spheroidizing equipment for spheroidizing, so that the spherical nickel powder with high uniformity and high spheroidization degree can be obtained.
The plasma spheroidizing equipment is industrial common equipment, and special plasma spheroidizing equipment is not required. Therefore, the preparation method of the invention can be seamlessly connected with the existing equipment, the production process is simple and convenient, and the product quality, the production efficiency and the like are obviously improved.
When the modified nickel powder coated by the graphene oxide is spheroidized in plasma spheroidizing equipment, the intrinsic thermal conductivity of the graphene oxide is recovered by high-temperature reduction of the graphene oxide, the graphene oxide is reduced at high temperature to play a role in heat conduction, the condition that the high-temperature thermal conductivity of nickel is insufficient is made up, and thus the spheroidizing degree of the nickel powder is increased.
In addition, the large surface binding energy difference between the high-temperature reduced graphene oxide and the nickel powder makes the interface acting force extremely weak, avoids the introduction of impurities in the nickel base in the whole process, and ensures the purity of the nickel powder after spheroidizing. Meanwhile, the existence of the high-temperature reduced graphene oxide also hinders the deposition growth of nickel molten drops, so that the granularity of the spheroidized nickel powder is refined, and the uniformity is ensured.
Preferably, in the step 103, the oscillation frequency of the plasma spheroidizing device is 4MHz, the plasma anode power is 20-26 KW, the powder feeding amount is 16-54 g/min, and the carrier gas is H2Or N2The air supply amount is 0.3 to 0.4m3H, Ar as a side gas and 5.0m of gas delivery3The central gas is Ar, the gas supply amount is 1.0-1.5 m3/h。
Specifically, when spheroidizing modified nickel powder coated with graphene oxide by using plasma spheroidizing equipment, the operating parameters of the plasma spheroidizing equipment are optimized, the oscillation frequency is preferably 4MHz, the plasma anode power is preferably 20-26 KW, and the powder feeding amount is preferably 16-54 g/min. Meanwhile, the carrier gas is preferably H2Or N2The preferred air supply amount is 0.3-0.4 m3The side gas is preferably Ar, and the gas supply amount is preferably 5.0m3The central gas is preferably Ar, and the gas delivery amount is preferably 1.0-1.5 m3/h。
The parameters in the plasma spheroidization process need to be matched cooperatively to determine the quality of the spheroidization effect. In the actual implementation process, each parameter value is adjusted according to the modified nickel powder coated by the graphene oxide with different particle size distributions, and the factors of the flow field and the gravitational field are combined to ensure that the powder enters a plasma torch of the plasma spheroidizing device at a position with higher and more uniform temperature, so that the heat is transmitted in place.
Meanwhile, the effective matching of the air supply amount and the powder supply amount can also increase the distribution of the powder in the effective heating area. When the powder feeding amount is small, the number of powder particles per unit volume is small, and only a part of the powder in the effective heating area is caused by the flow field effect, resulting in a limited spheroidizing effect. The spheroidizing effect is best when the quantity of powder particles per unit volume is increased along with the increase of the powder feeding quantity and the heat balance is gradually achieved. When the powder feeding amount is too large, the heat provided by the plasma torch of the plasma spheroidizing device is not enough to melt all the powder, and the flow field effect or the powder movement track is disordered, so that part of irregular powder particles are formed.
When a smaller air supply amount is used, the spheroidization degree is limited due to the flow field effect. When the air supply amount is further increased to the above preferable value, the spheroidization effect is good. When the air supply amount is further increased, irregular powder particles are found in the powder in a larger amount.
Therefore, the plasma spheroidizing equipment adopts the optimized parameters, so that the spheroidizing effect and the spheroidizing yield are ensured.
It should be noted that the above-mentioned embodiments of the method are described as a series of actions for simplicity of description, but those skilled in the art should understand that the present invention is not limited by the described sequence of actions. Further, those skilled in the art will appreciate that the embodiments described in the specification are presently preferred and that no particular act is required to implement the invention.
The embodiment of the invention also provides spherical nickel powder, which is prepared by the preparation method of the spherical nickel powder in any one of the embodiments.
Referring to fig. 2, fig. 2 is a scanning electron microscope image of spherical nickel powder prepared by the method for preparing spherical nickel powder according to the embodiment of the present invention.
As can be seen from FIG. 2, the spherical nickel powder has good spheroidization degree and high sphericity and uniformity, and can effectively meet the use requirements in the 3D printing process.
Further, the degree of the entire spheroidization treatment can be evaluated by the sphericity ratio and the sphericity yield.
The spheroidization ratio of the powder, i.e., the ratio of the number of spherical powders to the total number of powders. In order to truly reflect the spheroidization effect of the powder particles, 5 areas are randomly extracted from SEM pictures of powder shapes under different multiples to count the spheroidization rate alpha of the powder under different powder feeding rates. The calculation formula of the powder spheroidization rate alpha is as follows:
α=N0/N×100%（1）
in the formula, N0And N is the number of spherical powder particles and the total number of powder particles in a unit area, respectively.
The yield of the spherical powder is the ratio of the mass of the spherical powder in the collection tank of the plasma spheroidization device to the mass of the raw powder in the plasma torch of the plasma spheroidization device in a certain powder feeding time. In order to truly reflect the yield of the spherical powder, the powder feeding time t of each group of experiments is recorded, and the calculation method of the yield beta is as follows:
β=m/V*t×100%（2）
wherein V is the powder feeding speed, and m is the mass of the spherical powder in the collecting tank.
The sphericity degree of the spherical nickel powder is better, the sphericity degree and the uniformity degree are high, and the use requirements in the 3D printing process can be effectively met.
In addition, the embodiment of the invention also provides application of the spherical nickel powder prepared by the preparation method of any one of the above embodiments in a 3D printing process.
The spherical nickel powder has the advantages of high nodularity, good sphericity and high uniformity, and can be well applied to a 3D printing process.
In conclusion, the modification of the nickel powder by the graphene oxide is realized through the electrostatic adsorption effect, the problem of poor high-temperature thermal conductivity of the nickel powder can be effectively solved through the adhesion of the graphene on the surface layer of the graphene, the universality of the graphene spheroidizing device is high, the intrinsic thermal conductivity of the graphene oxide is recovered through the high-temperature reduction of the graphene oxide in the subsequent plasma spheroidizing, the situation that the high-temperature thermal conductivity of the nickel is insufficient is solved through the heat conduction effect of the high-temperature reduced graphene oxide, and the spheroidizing degree of the nickel powder can be effectively increased. Meanwhile, the interface acting force of the high-temperature reduction oxidized graphene and nickel is extremely weak due to the large surface binding energy difference between the high-temperature reduction oxidized graphene and the nickel, the introduction of graphene impurities in the nickel base is avoided in the whole process, the purity of the nickel powder after spheroidizing is ensured, and the uniformity is ensured while the granularity is refined.
For further understanding of the present invention, the following will specifically describe the method for preparing spherical nickel powder according to the present invention with reference to specific examples.
Example one
Adding a cationic surfactant (a silane coupling agent KH 550) into ethanol, and stirring for 10min to obtain a solution system containing the cationic surfactant; placing the electrolytic nickel powder in a prepared solution system containing a cationic surfactant at 60 ℃, stirring for 30min to complete modification of the electrolytic nickel powder, and washing with an ethanol solution to obtain modified nickel powder; wherein the mass ratio of the cationic surfactant (silane coupling agent KH 550) to the nickel powder (electrolytic nickel powder) is 1: 10.
And adding the modified nickel powder into the graphene oxide dispersion liquid under low-speed stirring to obtain the modified nickel powder coated by the graphene oxide. Wherein the mass ratio of the graphene oxide to the modified nickel powder in the graphene oxide dispersion liquid is 2: 1000.
And placing the modified nickel powder coated by the graphene oxide in plasma spheroidizing equipment for spheroidizing to obtain the spherical nickel powder. Wherein the oscillation frequency of the plasma spheroidizing equipment is 4MHz, the power of a plasma anode is 25KW, the powder feeding amount is 30g/min, and the carrier gas is N2The air supply amount is 0.35m3H, Ar as a side gas and 5.0m of gas delivery3H, central gas is Ar, air supply is 1.2m3/h。
Example two
Adding a cationic surfactant (a silane coupling agent KH 560) into ethanol, and stirring for 15min to obtain a solution system containing the cationic surfactant; putting the carbonyl nickel powder into a prepared 65 ℃ solution system containing the cationic surfactant, stirring for 20min to finish the modification of the carbonyl nickel powder, and washing with an ethanol solution to obtain modified nickel powder; wherein the mass ratio of the cationic surfactant (silane coupling agent KH 560) to the nickel powder (nickel carbonyl powder) is 2: 10.
And adding the modified nickel powder into the graphene oxide dispersion liquid under low-speed stirring to obtain the modified nickel powder coated by the graphene oxide. Wherein the mass ratio of the graphene oxide to the modified nickel powder in the graphene oxide dispersion liquid is 3: 1000.
And placing the modified nickel powder coated by the graphene oxide in plasma spheroidizing equipment for spheroidizing to obtain the spherical nickel powder. Wherein the oscillation frequency of the plasma spheroidizing device is 4MHz, and the power of the plasma anode is 20KW, powder feeding amount is 40g/min, and carrier gas is N2The air supply amount is 0.3m3H, Ar as a side gas and 5.0m of gas delivery3H, central gas is Ar, air supply is 1.5m3/h。
EXAMPLE III
Adding a cationic surfactant (a silane coupling agent KH 570) into ethanol, and stirring for 20min to obtain a solution system containing the cationic surfactant; placing the reduced nickel powder in a prepared 65 ℃ solution system containing a cationic surfactant, stirring for 30min to finish the modification of the reduced nickel powder, and washing with an ethanol solution to obtain modified nickel powder; wherein the mass ratio of the cationic surfactant (silane coupling agent KH 570) to the nickel powder (reduced nickel powder) is 3: 40.
And adding the modified nickel powder into the graphene oxide dispersion liquid under low-speed stirring to obtain the modified nickel powder coated by the graphene oxide. Wherein the mass ratio of the graphene oxide to the modified nickel powder in the graphene oxide dispersion liquid is 5: 1000.
And placing the modified nickel powder coated by the graphene oxide in plasma spheroidizing equipment for spheroidizing to obtain the spherical nickel powder. Wherein the oscillation frequency of the plasma spheroidizing equipment is 4MHz, the power of a plasma anode is 26KW, the powder feeding amount is 50g/min, and the carrier gas is N2The air supply amount is 0.4m3H, Ar as a side gas and 5.0m of gas delivery3H, central gas is Ar, air supply is 1.3m3/h。
Example four
Adding a cationic surfactant (melamine) into ethanol at 25 ℃, and stirring for 10min to prepare a solution system containing the cationic surfactant; placing the electrolytic nickel powder in a prepared solution system containing a cationic surfactant at 60 ℃, stirring for 30min to complete modification of the electrolytic nickel powder, and washing with an ethanol solution to obtain modified nickel powder; wherein the mass ratio of the cationic surfactant (melamine) to the nickel powder (electrolytic nickel powder) is 1: 10.
And adding the modified nickel powder into the graphene oxide dispersion liquid under low-speed stirring to obtain the modified nickel powder coated by the graphene oxide. Wherein the mass ratio of the graphene oxide to the modified nickel powder in the graphene oxide dispersion liquid is 2: 1000.
And placing the modified nickel powder coated by the graphene oxide in plasma spheroidizing equipment for spheroidizing to obtain the spherical nickel powder. Wherein the oscillation frequency of the plasma spheroidizing equipment is 4MHz, the power of a plasma anode is 25KW, the powder feeding amount is 30g/min, and the carrier gas is N2The air supply amount is 0.35m3H, Ar as a side gas and 5.0m of gas delivery3H, central gas is Ar, air supply is 1.2m3/h。
EXAMPLE five
Adding cationic surfactant (octadecyl trimethyl ammonium chloride) into ethanol at 40 deg.C, stirring for 15min, and preparing to obtain solution system containing cationic surfactant; putting the carbonyl nickel powder into a prepared 65 ℃ solution system containing the cationic surfactant, stirring for 20min to finish the modification of the carbonyl nickel powder, and washing with an ethanol solution to obtain modified nickel powder; wherein the mass ratio of the cationic surfactant (silane coupling agent KH 560) to the nickel powder (nickel carbonyl powder) is 2: 10.
And adding the modified nickel powder into the graphene oxide dispersion liquid under low-speed stirring to obtain the modified nickel powder coated by the graphene oxide. Wherein the mass ratio of the graphene oxide to the modified nickel powder in the graphene oxide dispersion liquid is 3: 1000.
And placing the modified nickel powder coated by the graphene oxide in plasma spheroidizing equipment for spheroidizing to obtain the spherical nickel powder. Wherein the oscillation frequency of the plasma spheroidizing equipment is 4MHz, the power of a plasma anode is 20KW, the powder feeding amount is 40g/min, and the carrier gas is N2The air supply amount is 0.3m3H, Ar as a side gas and 5.0m of gas delivery3H, central gas is Ar, air supply is 1.5m3/h。
Comparative example 1
The preparation method of the spherical nickel powder related to the comparative example adopts plasma spheroidizing equipment to spheroidize the nickel powder, and the nickel powder is similar to the first example, except that the steps of adding the nickel powder into a solution system of a cationic surfactant and adding graphene oxide dispersion liquid for modification are not carried out.
Comparative example No. two
The preparation method of the spherical nickel powder related to the comparative example adopts plasma spheroidizing equipment to spheroidize the nickel powder, and the nickel powder is similar to the second example, except that the steps of adding the nickel powder into a solution system of a cationic surfactant and adding graphene oxide dispersion liquid for modification are not carried out.
Comparative example No. three
The preparation method of the spherical nickel powder related to the comparative example adopts plasma spheroidizing equipment to spheroidize the nickel powder, and the nickel powder is similar to the third example, except that the steps of adding the nickel powder into a solution system of a cationic surfactant and adding graphene oxide dispersion liquid for modification are not carried out.
< evaluation of spheroidization degree of Nickel powder >
The spheroidization rates and spheroidization yields of the spherical nickel powders prepared in the above examples one to five and those prepared in the comparative examples one to three were measured in the above-described test manner, and the results are shown in the following tables.
Comparing the spherical nickel powders prepared in the first to fifth examples and the first to third comparative examples, it is found that the spherical nickel powders with high uniformity and high sphericity are prepared in the first to fifth examples on the premise of ensuring the spheroidization yield, while the sphericity of the spherical nickel powders prepared in the first to third comparative examples is much worse, the spheroidization degree of the nickel powders is effectively increased by adding the nickel powders into the solution system of the cationic surfactant and adding the graphene oxide dispersion liquid for modification, and the introduction of the graphene oxide does not affect the purity of the nickel powders.
In summary, according to the spherical nickel powder and the preparation method and the application thereof provided by the embodiment of the invention, the graded nickel powder to be treated is added into a solution system containing a cationic surfactant for modification to obtain the modified nickel powder; adding the modified nickel powder into the graphene oxide dispersion liquid, so that graphene oxide is attached to the surface of the modified nickel powder, and obtaining modified nickel powder coated by graphene oxide; and finally, spheroidizing the modified nickel powder coated by the graphene oxide by using plasma spheroidizing equipment to obtain the spherical nickel powder with high uniformity and high spheroidization degree.
According to the invention, the modification of the nickel powder by the graphene oxide is realized through the electrostatic adsorption effect, the problem of poor high-temperature heat conductivity of the nickel powder can be effectively solved by the adhesion of the graphene on the surface layer of the graphene, the universality of plasma spheroidizing equipment is high, the intrinsic heat conductivity of the graphene oxide is recovered by high-temperature reduction of the graphene oxide in the subsequent plasma spheroidizing, the condition of insufficient high-temperature heat conductivity of the nickel is compensated by the heat conduction effect of the high-temperature reduced graphene oxide, and the spheroidizing degree of the nickel powder can be effectively increased. Meanwhile, the large surface binding energy difference between the high-temperature reduction graphene oxide and the nickel ensures that the interface acting force is extremely weak, the whole process avoids the introduction of impurities in the nickel base, ensures the purity of the nickel powder after spheroidization, can also block the deposition growth of nickel molten drops, refines the granularity of the nickel powder after spheroidization, and ensures the uniformity.
In the above embodiments of the present invention, the descriptions of the respective embodiments have respective emphasis, and for parts that are not described in detail in a certain embodiment, reference may be made to related descriptions of other embodiments.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (8)
1. A method for preparing spherical nickel powder, comprising:
adding the graded nickel powder to be treated into a solution system containing a cationic surfactant, and cleaning to obtain modified nickel powder;
adding the modified nickel powder into the graphene oxide dispersion liquid to obtain modified nickel powder coated by graphene oxide;
and spheroidizing the modified nickel powder coated by the graphene oxide by using plasma spheroidizing equipment to obtain the spherical nickel powder.
2. The method according to claim 1, wherein in the step of obtaining modified nickel powder, the nickel powder is selected from one or more of electrolytic nickel powder, carbonyl nickel powder, reduced nickel powder, and atomized nickel powder.
3. The method according to claim 1, wherein in the step of obtaining the modified nickel powder, the cationic surfactant is selected from one or more of silane coupling agent, melamine, cetyl trimethyl ammonium bromide, and stearyl trimethyl ammonium chloride.
4. The method according to claim 1, wherein in the step of obtaining the modified nickel powder, the mass ratio of the cationic surfactant to the nickel powder is 1 to 3:10 to 40.
5. The method according to claim 1, wherein in the step of obtaining the modified nickel powder, when preparing the solution system containing the cationic surfactant, the cationic surfactant is added to ethanol or water and stirred for 5 to 20 min.
6. The method according to claim 1, wherein in the step of obtaining the modified nickel powder, the classified nickel powder to be treated is added to a solution system containing a cationic surfactant at 25 to 65 ℃, stirred for 10 to 30min, and washed with an ethanol solution.
7. The method according to claim 1, wherein in the step of obtaining the modified nickel powder coated with graphene oxide, the mass ratio of the graphene oxide to the modified nickel powder is 2-5: 1000.
8. The method according to claim 1, wherein in the step of obtaining the spherical nickel powder, the oscillation frequency of the plasma sphering apparatus is 4MHz and the plasma anode power20-26 KW, powder feeding amount of 16-54 g/min, and carrier gas of H2Or N2The air supply amount is 0.3 to 0.4m3H, Ar as a side gas and 5.0m of gas delivery3The central gas is Ar, the gas supply amount is 1.0-1.5 m3/h。
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