CN116393707A - Preparation method of refractory entropy control material spherical powder for additive manufacturing - Google Patents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
- B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
- B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/06—Metallic powder characterised by the shape of the particles
- B22F1/065—Spherical particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
- B22F1/145—Chemical treatment, e.g. passivation or decarburisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/1003—Use of special medium during sintering, e.g. sintering aid
- B22F3/1007—Atmosphere
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/1017—Multiple heating or additional steps
- B22F3/1021—Removal of binder or filler
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
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Abstract
The invention relates to a preparation method of refractory entropy control material spherical powder for additive manufacturing, which comprises the following steps: firstly, dispersing slurry; secondly, spray drying; third, vacuum degreasing and sintering; and fourthly, plasma spheroidization. Further comprises a fifth step of classifying and screening. The refractory entropy control material provided by the invention comprises Ta, W and a variable element M; wherein M is one or more of Nb, zr, mo, hf, ti, re, V, and can also comprise nonmetallic element N, wherein N is C, B or Si. The preparation method of the refractory entropy control material powder provided by the invention has the advantages of simple and convenient flow, controllable process, less material loss, controllable morphology and particle size of the prepared refractory entropy control material powder, uniform components and high production efficiency, and realizes the technical breakthrough of macro preparation of the refractory entropy control material powder with low cost.
Description
Technical Field
The invention belongs to the field of refractory entropy control material powder preparation, and particularly relates to a preparation method of refractory entropy control material spherical powder for additive manufacturing.
Background
Additive manufacturing, commonly referred to as metal 3D printing, is a new manufacturing technique. The technology is based on a digital model, takes powder as a raw material, adopts laser, electron beam, a special wavelength light source, electric arc and the combination of various energy sources as high-energy heat sources, and utilizes the 'discrete-stacking' molding principle to manufacture a complex, compact, uniform and excellent-performance solid molded part.
The refractory entropy control material comprises a refractory medium-entropy alloy material, a refractory high-entropy alloy material, a high-entropy ceramic material and a high-entropy composite material, belongs to a high-temperature structural material with very wide application prospect, and can avoid the difficult processing problem of the refractory entropy control material due to brittleness by using an additive manufacturing technology.
At present, the common preparation methods of refractory entropy control powder mainly comprise mechanical alloying, rotating electrodes, melt atomization and the like. As patent CN202011304272.2 discloses a WMoTaTi high-entropy alloy powder prepared by high-energy ball milling technology, the powder alloying degree is good, but the ball milling time as long as 60 hours severely limits the production efficiency of the high-entropy alloy powder, and it is difficult to realize batch preparation of the powder. Patent CN201711397084.7 discloses a process for preparing CoCrMo spherical powder based on a rotating electrode process, but according to patent CN201611174427.9, the preparation process of an electrode rod for a rotating electrode is complex, and the process is more difficult and complicated for high-melting-point elements, has high cost, and limits the mass production of refractory high-entropy powder. Patent 202011254788.0 discloses a technology for preparing refractory high-entropy alloy powder by obtaining a refractory high-entropy alloy cast ingot through high-vacuum arc melting, then carrying out hydrogenation crushing, vibration grinding and plasma spheroidization on the cast ingot, wherein the method can be used for preparing refractory metal spherical powder, but the process for preparing refractory high-entropy alloy with larger size through arc melting is complex, the cost is higher, the cast ingot is influenced by cooling of a water-cooled copper crucible, the cast ingot is extremely easy to have the phenomena of component segregation and uneven structure, and the quality of the powder is influenced. It can be seen from the above patents that refractory entropy control materials have very high melting points and that research for additive manufacturing has progressed slowly.
Therefore, obtaining high-quality powder with uniform components, high sphericity, controllable particle size and good morphology becomes a problem to be solved urgently.
Disclosure of Invention
In order to solve the problems, the invention aims to provide a preparation method of refractory entropy control material spherical powder for additive manufacturing, and the refractory entropy control material powder prepared by the method has the advantages of controllable morphology and particle size, uniform components, less material loss and high production efficiency.
In order to achieve the above object, the present invention provides a method for preparing spherical powder of refractory entropy control material for additive manufacturing, comprising the steps of:
in the first step, slurry dispersion:
after the refractory entropy control material raw material powder is calculated according to mole fraction, the refractory entropy control material raw material powder is converted into mass fraction for proportioning, and then the mass fraction and sol liquid are put into a colloid disperser for mixing to obtain slurry;
the colloid disperser can not only effectively refine the raw material powder, but also avoid sedimentation and layering of the powder due to different densities, thereby obtaining suspension slurry with evenly dispersed powder particles.
Second, spray drying:
feeding the slurry into a closed airflow spray drying device, atomizing the slurry into fine liquid drops, drying the fine liquid drops to form porous agglomerated powder, and collecting the porous agglomerated powder through a cyclone separator;
in order to avoid the sedimentation of the powder due to different densities and influence the uniformity of the porous agglomerated powder, the slurry is stirred in real time by utilizing magnetic stirring in the spray drying process.
The closed airflow type spray drying system can regulate and control the aperture of the nozzle to control the particle size of the porous agglomerated powder according to the requirement of additive forming.
Third, vacuum degreasing sintering:
placing the collected porous agglomerated powder into a vacuum furnace for degreasing and sintering to obtain degreased and sintered powder;
the vacuum degreasing sintering can remove carbon, oxygen and other impurity elements introduced by the binder, so that the elemental metals in contact with each other are subjected to solid diffusion to a certain extent, the internal combination of the agglomerated powder is increased, and the fluidity of the powder before plasma spheroidization is improved;
fourth, plasma spheroidization:
the degreased sintering powder is sent into plasma spheroidizing equipment for spheroidizing treatment, the refractory entropy control material powder is obtained, and the particle size range of the powder is 5-150 mu m.
Still further, the method further comprises: fifth step, classifying and screening:
and screening the refractory entropy control material powder according to the additive manufacturing requirement, and vibrating for 300 seconds to obtain the screened refractory entropy control material powder.
The porous agglomerated powder after spray drying can be fused rapidly to obtain compact spherical powder of the multi-component complex-component refractory entropy control material, and the powder is classified and screened according to the requirement of additive forming equipment on the particle size of the powder.
The spherical powder of the refractory entropy control material can be obtained by plasma spheroidization, and the grading screening is to screen the particle size according to the requirements of different additive forming equipment.
Still further, the refractory entropy control material comprises Ta, W and a variable element M; wherein M is one or more of Nb, zr, mo, hf, ti, re, V; the refractory entropy control material has a chemical formula (TaW) M x Wherein x represents a molar ratio and x=0 to 2, and the molar fraction of each component is 5 to 35%.
Still further, the refractory entropy control material further comprises a nonmetallic element N; wherein N is C, B or Si; the refractory entropy control material has a chemical formula (TaW) M y Nz is represented where y, z are molar ratios and y=0 to 2, z=0 to 1.5, and the molar fraction of each component is 5 to 35%.
PreferablyIn the refractory entropy control material, ta is Ta metal simple substance, W is W metal simple substance, mo is Mo metal simple substance, ti is Ti metal simple substance, re is Re metal simple substance, V is V metal simple substance, zr is ZrH 2 Hf HfH 2 The method comprises the steps of carrying out a first treatment on the surface of the All the raw materials are powder, and the particle size of the powder is 0.1-3 mu m.
The raw materials C, B or Si are all simple substance powder, wherein the simple substance powder C is graphite, and the particle size of the powder is 0.1-3 mu m.
Because the elemental Zr and Hf metal powder is very active and has high storage and use risks, the Zr and Hf elements are ZrH respectively 2 And HfH 2 The metal hydride form is stored and used. Although each metal simple substance is a refractory element, the difference of melting point and density is easy to cause uneven sedimentation of mixed powder and asynchronous fusion during plasma spheroidization, this brings considerable difficulty to the preparation of spherical powder, so that all raw material powder particle sizes are controlled to 0.1 to 3 μm for optimum preparation.
Further, the sol liquid is prepared by dissolving polyvinyl alcohol, ammonium polyacrylate and sodium lignosulfonate in absolute ethyl alcohol; wherein the mass fraction of the polyvinyl alcohol in the sol solution is 2-6wt%, the mass fraction of the ammonium polyacrylate in the sol solution is 0.1-3.0wt%, and the mass fraction of the sodium lignosulfonate in the sol solution is 0-2wt%.
In the sol solution, polyvinyl alcohol is used as a binder, ammonium polyacrylate is used as a dispersing agent, and sodium lignosulfonate is used as a defoaming agent.
Further, the solid content of the slurry obtained by mixing in the first step is 30-70 wt%; the rotation speed of the colloid disperser is 2900r/min, and the time is 15min.
The solid in the solid content of the slurry is refractory entropy control material raw material powder, and the rest is sol liquid.
The short-time dispersion can obtain a slurry which is uniformly mixed and refined.
Further, in the second step, a peristaltic pump is further adopted to send the slurry into a closed airflow type spray drying device, and magnetic stirring is performed at the same time; the spray drying conditions were: the caliber of the nozzle of the closed airflow spray drying equipment is 0.5 to the upper2.0mm, inlet temperature of 150-250 ℃, outlet temperature of 100-150 ℃, atomization pressure of 0.05-1.2 MPa, feeding rate of 1500-2500 mL/h, refrigerating fluid temperature of 10-20 ℃, condensing air outlet temperature of 10-20 ℃, and setting protective gas as Ar or N 2 。
Magnetic stirring is used to avoid sedimentation and delamination of the raw material powder due to density differences. The shielding gas is used to avoid oxidation of the refractory metal.
Further, the specific operation in the third step is as follows: placing the spray-dried powder into a vacuum heating furnace, and introducing protective gas Ar or N 2 Then the temperature is raised from room temperature to T at 10 ℃ per minute 1 Temperature at T 1 Preserving heat for 1-4 h at the temperature, then from T 1 The temperature is raised to T at 5 ℃/min 2 Temperature at T 2 Preserving heat for 2-6 h at the temperature, and then cooling to room temperature along with a furnace, wherein the T is 1 The temperature is 400-600 ℃, T 2 The temperature range is 1000-1400 ℃.
This step is a necessary process to obtain a powder having excellent fluidity and low carbon-oxygen impurity content.
Further, the fourth step plasma spheroidization control conditions are: the running power of the equipment is 10-85 kW, the argon flow is 30-200 slpm, the hydrogen flow is 2-20 slpm, and the powder feeding rate is 10-60 g/min.
The step is a necessary process for obtaining spherical powder, the spray-dried agglomerated porous powder can be fused rapidly under a high-temperature plasma torch, compact spherical powder is obtained, and the spherical refractory entropy control material powder is obtained through a collecting and preparing system, wherein the diameter of the powder is controllable within the range of 5-150 mu m.
According to the invention, the raw material powder and the sol liquid are mixed by the colloid disperser, so that suspension slurry which is thinned and powder particles are uniformly dispersed can be obtained in a short time; directly pouring the uniformly dispersed slurry into spray drying equipment without further treatment to form spherical porous agglomerated powder; then placing the porous agglomerated powder into a vacuum furnace for degreasing and sintering; and finally, delivering the degreased and sintered porous agglomerated powder into plasma spheroidizing equipment to obtain the multi-component complex-component refractory entropy control material spherical compact powder, wherein the particle size range of the powder can be obtained by adjusting the nozzle aperture of spray drying equipment and can be controlled within the range of 5-150 mu m.
The powder prepared by the invention is classified and screened according to the requirements of additive forming equipment on the particle size of the powder, for example, the particle size of the powder for laser cladding deposition is between 30 and 105 mu m, the particle size of the powder for selective laser melting is between 15 and 53 mu m, the particle size of the powder for electron beam additive manufacturing is between 45 and 106 mu m, and the particle size of the powder for cold spraying additive manufacturing is between 6 and 45 mu m.
The spray drying equipment used in the invention is closed airflow spray drying equipment, and different from other spray drying modes, the closed airflow spray drying tower can obtain powder particles with wider particle size distribution range by adjusting spray drying process parameters and nozzle caliber, the particle size of the powder is more flexibly controlled, the operation and the control are easy, and the spray drying equipment is suitable for preparing multi-component refractory entropy control material spherical powder with different particle sizes.
The invention is characterized in that:
1. the invention can realize the preparation of the spherical powder of the multi-component refractory entropy control material, and the prepared powder has good sphericity, uniform components, smooth surface, compact structure, low impurity content and controllable granularity;
2. compared with a mechanical alloying method, the invention abandons the traditional ball milling process, does not need to carry out high-energy ball milling process for a plurality of days, has high production efficiency, and overcomes the pollution of grinding balls and grinding tank impurities to products in the mechanical alloying method. In addition, the spray drying process of evenly dispersing the feeding and the powder avoids material loss, and the powder utilization rate is high;
3. compared with a smelting-crushing-spheroidizing method, the method avoids the phenomenon of nonuniform powder structure caused by segregation of cast ingot components;
4. compared with a plasma rotary electrode atomization method, the method provided by the invention has the advantages that alloy rods are not required to be prepared, the refractory entropy control material powder can be prepared only by a relatively simple process flow, and the process is simple.
5. The invention effectively solves the problem of uneven powder components caused by precipitation of multi-component refractory metal particles in slurry. Refractory metal components are of great specific gravity and of great difference, and there are different degrees of aggregate sedimentation in the solvent, resulting in non-uniformity of the slurry composition. According to the invention, aiming at the characteristics of the multi-component refractory metal, polyvinyl alcohol is preferably used as a binder and ammonium polyacrylate is preferably used as a dispersing agent, and the proportion of the polyvinyl alcohol (binder) and the ammonium polyacrylate (dispersing agent) is optimized, so that the charge condition of the surface adsorption of the dispersed multi-component particles in the slurry is regulated and controlled, the aggregation and dispersion state of the multi-component refractory metal particles in the slurry is improved, the conditions of adhesion, aggregation, sedimentation, layering and the like of the multi-component refractory metal particles in the slurry are prevented, and the uniformity and stability of the slurry are improved.
6. Compared with the centrifugal spray drying mode (the particle size of the powder is controlled by the centrifugal rotating speed and is limited by the centrifugal rotating speed, so that the particle size range of the powder is relatively concentrated), the invention adopts closed airflow type spray drying, powder particles (5-150 mu m) with wider particle size distribution range can be obtained by regulating and controlling spray drying process parameters and nozzle caliber, the particle size of the powder can be flexibly controlled, the operation is simple and easy to control, and the method is suitable for the batch production of complex multi-component refractory entropy control material spherical powder with a plurality of particle size ranges.
7. The method has the advantages that organic matters in the binder are removed through the degreasing sintering process, the impurity content of C, O and the like is reduced, the purity of the powder is improved, the bonding state of the multi-component refractory metal particles is improved, the fluidity of the powder is improved, and the next plasma spheroidizing process is conveniently and smoothly developed.
The invention has the beneficial effects that:
the invention provides a preparation method of refractory entropy control material spherical powder for additive manufacturing, which has the advantages of controllable morphology and particle size, uniform components, less material loss and high production efficiency, and adopts the technological processes of spray drying, vacuum degreasing sintering and plasma spheroidization to realize the large-scale preparation of the refractory entropy control material spherical powder with high sphericity, good fluidity, controllable particle size and low cost.
Drawings
Fig. 1 is a flowchart of a method for preparing a spherical powder of a refractory entropy control material for additive manufacturing according to the present invention.
Fig. 2 shows the morphology of NbTaW agglomerated powder prepared by closed air-flow spray drying according to example 1 of the present invention.
FIG. 3 is a graph showing the particle size distribution of NbTaW agglomerated powder prepared by closed air-flow spray drying in example 1 of the present invention.
Fig. 4 is a graph showing the powder morphology of the NbTaW refractory entropy control material prepared in example 1 of the present invention.
Fig. 5 is a cross section and an element distribution diagram of an NbTaW refractory entropy control material powder prepared in example 1 of the present invention.
FIG. 6 is a surface morphology of NbMoTaWZr agglomerated powder prepared in example 3 of the present invention.
FIG. 7 is a graph showing the elemental profile of the cross-section of an NbMoTaWZr agglomerate prepared in example 3 according to the present invention.
FIG. 8 is a graphical representation of a powder of a NbMoTaWZr refractory entropy control material prepared in example 3 of the present invention.
FIG. 9 is a phase diagram of a powder of a refractory entropy control material of NbMoTaWZr prepared in example 3 of the present invention.
Detailed Description
The following examples are set forth to provide a more thorough and complete description of the present invention, and to enable those skilled in the art to more readily understand the advantages and features of the present invention, and to provide a more readily apparent and definitive definition of the scope of the present invention, but are not intended to limit the scope of the present invention.
Unless otherwise specified, the reagents and raw materials described in the examples of the present application are all commercially available.
Apparatus and method for controlling the operation of a device
The colloid dispenser was model Jiang Zhong JM-L50.
The closed airflow type spray drying equipment is an Shanghai elegance closed YC-018A organic solvent spray dryer.
Degreasing-sintering furnaces were purchased from beijing pana vacuum equipment limited.
The plasma spheroidization apparatus is Teknano-15 of Tekna Plasma Systems inc.
The model of the ultrasonic powder sieving machine is an ultrasonic vibration controller CSB-1.
The laser particle sizer model is Mastersizer 3000.
The model of the oxygen-nitrogen-hydrogen analyzer is Leco and ON 736. The model of the carbon sulfur analyzer is Leco, CS 884.
The X-ray diffractometer model was Bruker D8.
The scanning electron microscope model is SEM, FEI Quanta 200F, and the spectrometer model is EDS, xploe 30.
EXAMPLE 1 preparation of NbTaW spherical powder
The NbTaW spherical powder is prepared by adopting the process flow shown in figure 1, and comprises the steps of classifying and screening, specifically:
(1) And (3) slurry dispersion:
the Nb metal simple substance powder (granularity is smaller than 3 mu m) with the purity of more than 99.9%, the Ta metal simple substance powder (granularity is smaller than 3 mu m) and the W metal simple substance powder (granularity is smaller than 3 mu m) are calculated according to the mole fraction, and are converted into mass fraction to be mixed, and then the mass fraction and the sol liquid are put into a colloid disperser to be uniformly mixed, so as to obtain suspension slurry with uniformly dispersed powder particles. The rotation speed of the colloid disperser is 2900r/min and the time is 15min. The solid phase content of the slurry is 50wt%, and the mass fraction of the binder is 4wt%; the dispersant in the sol solution is ammonium polyacrylate, and the mass fraction is 0.5wt%; the concentration of sodium lignosulfonate defoamer was 1.0wt%.
(2) Spray drying:
and (3) feeding the uniformly prepared and dispersed slurry into a spray dryer under the action of a peristaltic pump, atomizing the slurry into small liquid drops in the spray dryer, and then drying the small liquid drops into porous agglomerated powder. The slurry is sent into a spray dryer and magnetically stirred at the same time, so as to avoid sedimentation and delamination of raw material powder due to density difference. Nozzle bore of spray dryer: 0.5mm, the inlet temperature is 180 ℃, the outlet temperature is 130 ℃, the atomization pressure is 0.05MPa, the feeding rate is 1800mL/h, the temperature of the refrigerating fluid is 15 ℃, the condensing air outlet temperature is 15 ℃, and the protective gas Ar is introduced in spray drying to obtain the NbTaW refractory medium entropy alloy agglomerated powder in the example. The powder after spray drying was measured by an oxygen-nitrogen-hydrogen analyzer and a carbon-sulfur analyzer to have an oxygen content of about 3000ppm and a carbon content of about 1300ppm.
(3) Vacuum degreasing and sintering:
and (3) placing the spray-dried porous agglomerated powder into a vacuum furnace, and introducing protective gas Ar. Heating from room temperature to 500 ℃ at 10 ℃/min, preserving heat for 1h at the temperature of 500 ℃, then heating from 500 ℃ to 1300 ℃ at 5 ℃/min, preserving heat for 2h, and then cooling to room temperature along with a furnace to obtain the degreasing sintered powder. The oxygen content of the defatted sintered powder is about 800ppm, the carbon content is about 650ppm, and the content of impurities such as carbon, oxygen and the like after the defatted sintering is obviously reduced by the oxygen-nitrogen-hydrogen analyzer and the carbon-sulfur analyzer.
(4) Plasma spheroidization:
placing the degreased sintering powder into a plasma spheroidizing device which runs stably, and placing the degreased sintering powder into Ar and H 2 Spheroidization is carried out under protection to obtain the NbTaW spherical powder in the embodiment. The NbTaW spherical powder belongs to refractory medium entropy material powder in refractory entropy control materials.
The specific process of plasma spheroidization comprises the following steps: the power of the plasma torch is 45kW, the argon flow is 80slpm, the hydrogen flow is 2.5slpm, and the powder feeding rate is 15g/min.
Because the prepared refractory medium-entropy material powder is used for additive manufacturing, oxide with low melting point can be generated due to the fact that the oxygen content is too high, cracks in the cooling process are easy to generate, brittleness can be increased due to the fact that the carbon content is too high, and the plasticity of the material is affected. Therefore, the oxygen content and the carbon content of the powder after spheroidization in the embodiment are measured again, and the oxygen content of the powder after spheroidization is about 350ppm and the carbon content of the powder after spheroidization is about 450ppm measured by an oxygen-nitrogen-hydrogen analyzer and a carbon-sulfur analyzer, so that the additive manufacturing requirement is met.
In order to facilitate observation, nbTaW spherical powder is screened, if the material adding equipment is not determined, the preparation of the spherical powder is completed after plasma spheroidization, and screening is performed when the spherical powder is waiting for use.
(5) Classifying and screening:
according to the demand of additive manufacturing, an ultrasonic powder sieving machine (CSB-1 ultrasonic vibration controller) is utilized to sieve the obtained NbTaW refractory medium entropy spherical powder, and the vibration time is 300s.
FIG. 2 is a graph of the morphology of NbTaW agglomerated powder prepared by air-flow spray drying in example 1, wherein a) is the surface morphology on a 100 μm scale and b) is the surface morphology on a 10 μm scale. It can be seen from fig. 2 a) that most of the granulated powder has an approximately spherical morphology, with some fines present. And the complete sphericity of the granulated powder is better as can be clearly seen from figure 2 b).
Detecting path distribution by using a Mastersizer 3000 type laser diffraction particle size analyzer, and FIG. 3 shows a NbTaW particle size distribution diagram, wherein the abscissa Particle Diameter shows particle size, the ordinate Differential Volume shows different contents in terms of volume percentage, and the ordinate shows Cumulative (right)<Volume is the cumulative percentage. As can be seen from the particle size distribution of NbTaW spray-dried powder in FIG. 3, the particle size distribution range is wide, D 10 ＝6.94μm，D 50 ＝49.65μm，D 90 ＝82.58μm。
As can be seen from fig. 4, the powder surface of the refractory intermediate entropy material after the spheroidization of the NbTaW plasma spheroidization powder is smooth, the powder is compact, and the sphericity is good. From the cross-sectional morphology and element distribution diagram of the refractory medium entropy material powder after plasma spheroidization in fig. 5, it can be seen that the powder after spheroidization is compact and the composition is uniform and controllable.
Example 2 preparation of NbMoTaWC spherical powder
Adopts the process flow shown in figure 1 and comprises the steps of classifying and screening, specifically:
(1) And (3) slurry dispersion:
the Nb metal simple substance powder (granularity is less than 3 mu m), ta metal simple substance powder (granularity is less than 3 mu m), mo metal simple substance powder (granularity is less than 3 mu m) and WC powder (granularity is less than 3 mu m) with purity more than 99.9 percent are calculated to convert the mole fraction into mass fraction, and the mass fraction is mixed with sol liquid, and then the mixture is put into a colloid disperser to be mixed, so as to obtain suspension slurry with uniformly dispersed powder particles. The rotation speed of the colloid disperser is 2900r/min and the time is 15min. The solid phase content of the slurry is 45wt%, the mass fraction of the binder is 3.5wt%, the dispersing agent in the sol solution is ammonium polyacrylate, the mass fraction is 0.5wt%, and the concentration of the sodium lignosulfonate defoamer is 1.2wt%.
(2) Spray drying:
the evenly-dispersed slurry is filled in a peristaltic pumpUnder the action of the water, the slurry is fed into a spray dryer, atomized into small droplets in the spray dryer, and then dried into agglomerated powder. The slurry is sent to a spray dryer and magnetically stirred at the same time, so as to avoid sedimentation and delamination of raw material powder due to density difference. Nozzle bore of spray dryer: 0.5mm, inlet temperature of 250 ℃, outlet temperature of 145 ℃, atomization pressure of 0.08MPa, feeding rate of 2200mL/h, refrigerating fluid temperature of 13 ℃, condensing air outlet temperature of 15 ℃, and protective gas N is introduced in spray drying 2 The porous agglomerated powder of NbMoTaWC in this example was obtained. The powder oxygen content after spray drying was about 3300ppm as measured by an oxygen nitrogen hydrogen analyzer and a carbon sulfur analyzer.
(3) Vacuum degreasing and sintering:
and (3) placing the spray-dried porous agglomerated powder into a vacuum furnace, and introducing protective gas Ar. Heating from room temperature to 600 ℃ at 10 ℃/min, preserving heat for 1h at the temperature of 600 ℃, then heating from 600 ℃ to 1350 ℃ at 5 ℃/min, preserving heat for 4h, and then cooling to room temperature along with a furnace to obtain the degreasing sintered powder. The oxygen content of the defatted sintered powder was about 550ppm as measured by an oxygen-nitrogen-hydrogen analyzer.
(4) Plasma spheroidization:
placing the degreased sintering powder into a plasma spheroidizing device which runs stably, and placing the degreased sintering powder into Ar and H 2 Spheroidizing is carried out under protection to obtain the NbMoTaWC spherical powder in the embodiment. The NbMoTaWC spherical powder belongs to refractory high-entropy spherical powder in refractory entropy control materials.
The oxygen content of the refractory high-entropy spherical powder is about 300ppm measured by an oxygen-nitrogen-hydrogen analyzer, and the specific process of plasma spheroidization comprises the following steps: the power of the plasma torch is 55kW, the argon flow is 90slpm, the hydrogen flow is 3.5slpm, and the powder feeding rate is 20g/min.
(5) Classifying and screening:
according to the demand of additive manufacturing, an ultrasonic powder sieving machine (CSB-1 ultrasonic vibration controller) is utilized to sieve the obtained NbMoTaWC refractory high-entropy spherical powder, and the vibration time is 300s.
Example 3 preparation of NbMoTaWZr spherical powder
Adopts the process flow shown in figure 1 and comprises the steps of classifying and screening, specifically:
(1) And (3) slurry dispersion:
nb metal simple substance powder (particle size less than 3 μm), ta metal simple substance powder (particle size less than 3 μm), mo metal simple substance powder (particle size less than 3 μm), W metal simple substance powder (particle size less than 3 μm) and ZrH with purity of more than 99.9% 2 The powder (granularity is smaller than 3 mu m) is calculated to convert the mole fraction into the mass fraction for proportioning, and then the mass fraction and the sol liquid are put into a colloid disperser for mixing, so as to obtain suspension slurry with uniformly dispersed powder particles. The rotation speed of the colloid disperser is 2900r/min and the time is 15min. The solid phase content of the slurry is 50wt%, the mass fraction of the binder is 2.5wt%, and the concentration of the sodium lignosulfonate defoamer is 1.5wt%.
(2) Spray drying:
and (3) feeding the uniformly prepared and dispersed slurry into a spray dryer under the action of a peristaltic pump, atomizing the slurry into small liquid drops in the spray dryer, and then drying the small liquid drops into agglomerated powder. The slurry is sent into a spray dryer and magnetically stirred at the same time, so as to avoid sedimentation and delamination of raw material powder due to density difference. The spray drier has nozzle caliber of 0.5mm, inlet temperature of 200deg.C, outlet temperature of 150deg.C, atomization pressure of 0.06MPa, feeding rate of 2000mL/h, refrigerating fluid temperature of 18deg.C, condensing air outlet temperature of 16deg.C, and spray drying under N 2 The porous agglomerate powder of NbMoTaWZr in this example was obtained. The powder after spray drying was measured by an oxygen-nitrogen-hydrogen analyzer and a carbon-sulfur analyzer to have an oxygen content of about 6050ppm and a carbon content of about 2684ppm.
(3) Vacuum degreasing and sintering:
and (3) placing the spray-dried agglomerated powder into a vacuum furnace, and introducing protective gas Ar. Heating from room temperature to 550 ℃ at 10 ℃/min, preserving heat for 1h at the temperature of 550 ℃, then heating from 550 ℃ to 1400 ℃ at 5 ℃/min, preserving heat for 2h, and then cooling to room temperature along with a furnace to obtain the degreasing sintered powder. The oxygen content of the defatted sintered powder was about 850ppm and the carbon content was about 400ppm as measured by an oxygen-nitrogen-hydrogen analyzer and a carbon-sulfur analyzer, respectively.
(4) Plasma spheroidization:
stabilizing the defatted sintered powderIn the running plasma spheroidizing equipment, ar and H 2 Spheroidization is carried out under protection to obtain the NbMoTaWZr spherical powder in the embodiment. The NbMoTaWZr spherical powder belongs to refractory high-entropy spherical powder in refractory entropy control materials.
The specific process of plasma spheroidization comprises the following steps: the specific process of plasma spheroidization comprises the following steps: the power of the plasma torch is 40kW, the argon flow is 70slpm, the hydrogen flow is 1.5slpm, and the powder feeding rate is 28g/min.
The oxygen content of the refractory high-entropy spherical powder is about 750ppm and the carbon content is about 255ppm measured by an oxygen-nitrogen-hydrogen analyzer and a carbon-sulfur analyzer respectively.
In order to facilitate observation, nbMoTaWZr spherical powder is screened, if the material adding equipment is not determined, the preparation of the spherical powder is completed after plasma spheroidization, and screening is performed when the powder is waiting for use.
(5) Classifying and screening:
when in practical use, the sieving range is selected according to the requirement of additive manufacturing, and the obtained NbMoTaWZr refractory high-entropy spherical powder is sieved by an ultrasonic sieving machine (CSB-1 ultrasonic vibration controller) for 300s.
FIG. 6 is a surface topography of the NbMoTaWZr porous agglomerated powder prepared in example 3, wherein a) is the surface topography under the 100 μm scale, and b) is the surface topography under the 10 μm scale. From fig. 6 a) it can be seen that the sphericity of the porous agglomerated powder is high, no satellite spheres are present, and the enlarged morphology of the individual porous agglomerated powder fig. 6 b) also verifies this conclusion.
The cross-sectional elemental plane distribution of the NbMoTaWZr porous agglomerated powder was photographed using a scanning electron microscope-energy spectrometer as shown in fig. 7. As can be seen from fig. 7, the composition is uniformly controllable. From the microscopic morphology graph of the NbMoTaWZr refractory high-entropy spherical powder shown in FIG. 8, the surface of the spheroidized powder is smooth, the powder is compact, and the sphericity is good. Fig. 9 is a phase diagram of a NbMoTaWZr refractory high entropy spherical powder, and as can be seen from fig. 9, the powder has high purity without other impurities such as oxide.
According to the embodiment, the refractory entropy control material powder prepared by the method has controllable morphology and particle size, uniform components, less material loss and high production efficiency, and the technological processes of spray drying, vacuum degreasing sintering and plasma spheroidization are utilized to realize the large-scale preparation of the refractory entropy control material powder with high sphericity, good fluidity, controllable particle size and low cost.
The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the refractory entropy control material spherical powder for additive manufacturing is characterized by comprising the following steps of:
in the first step, slurry dispersion:
after the refractory entropy control material raw material powder is calculated according to mole fraction, the refractory entropy control material raw material powder is converted into mass fraction for proportioning, and then the mass fraction and sol liquid are put into a colloid disperser for mixing to obtain slurry;
second, spray drying:
feeding the slurry into a closed airflow type spray drying device, atomizing the slurry into fine liquid drops, drying the fine liquid drops to form porous agglomerated powder, collecting the porous agglomerated powder through a cyclone separator, and stirring the slurry in real time by using magnetic stirring in the spray drying process;
third, vacuum degreasing sintering:
placing the collected porous agglomerated powder into a vacuum furnace for degreasing and sintering to obtain degreased and sintered powder;
fourth, plasma spheroidization:
and (3) delivering the degreased and sintered powder into plasma spheroidizing equipment for spheroidizing treatment to obtain refractory entropy control material powder, wherein the particle size range of the powder is 5-150 mu m.
2. The method for preparing a spherical powder of refractory entropy control material for additive manufacturing according to claim 1, further comprising, after the fourth step: fifth step, classifying and screening: and screening the refractory entropy control material powder according to the additive manufacturing requirement, and vibrating for 300 seconds to obtain the screened refractory entropy control material powder.
3. The method for producing a spherical powder of a refractory entropy control material for additive manufacturing according to claim 1 or 2, wherein the refractory entropy control material comprises Ta, W and a variable element M; wherein M is one or more of Nb, zr, mo, hf, ti, re, V; the refractory entropy control material has a chemical formula (TaW) M x Wherein x represents a molar ratio and x=0 to 2, and the molar fraction of each component is 5 to 35%.
4. A method of preparing a spherical powder of refractory entropy control material for additive manufacturing as recited in claim 3, wherein the refractory entropy control material further comprises a nonmetallic element N; n is C, B or Si; the refractory entropy control material has a chemical formula (TaW) M y Nz is represented by the mole ratio of y to z, and y=0 to 2, and z=0 to 1.5.
5. The method for preparing spherical powder of refractory entropy control material for additive manufacturing according to claim 3 or 4, wherein Ta raw material is Ta metal simple substance powder, W raw material is W metal simple substance powder, mo raw material is Mo metal simple substance powder, ti raw material is Ti metal simple substance powder, re raw material is Re metal simple substance powder, V raw material is V metal simple substance powder, zr raw material is ZrH 2 Powder, hf raw material HfH 2 A powder; the nonmetallic elements C, B, si are all simple substance powder, wherein the simple substance powder C is graphite, and the powder particle size of the raw materials is 0.1-3 mu m.
6. The method for preparing the refractory entropy control material spherical powder for additive manufacturing according to claim 1, wherein the sol is prepared by dissolving polyvinyl alcohol, ammonium polyacrylate and sodium lignosulfonate in absolute ethyl alcohol; wherein the mass fraction of the polyvinyl alcohol in the sol solution is 2-6wt%, the mass fraction of the ammonium polyacrylate in the sol solution is 0.1-3.0wt%, and the mass fraction of the sodium lignosulfonate in the sol solution is 0-2wt%.
7. The method for preparing spherical powder of refractory entropy control material for additive manufacturing according to claim 1, wherein the solid content in the slurry obtained by mixing in the first step is 30-70 wt%; the rotation speed of the colloid disperser is 2900r/min, and the time is 15min.
8. The method for preparing spherical powder of refractory entropy control material for additive manufacturing according to claim 1, wherein in the second step, a peristaltic pump is further used to feed the slurry into a closed air flow type spray drying device while magnetic stirring is performed; the spray drying conditions were: the aperture of a nozzle of the closed airflow type spray drying equipment is 0.5-2.0 mm, the inlet temperature is 150-250 ℃, the outlet temperature is 100-150 ℃, the atomization pressure is 0.05-1.2 MPa, the feeding rate is 1500-2500 mL/h, the temperature of a refrigerating fluid is 10-20 ℃, the temperature of condensing air outlet is 10-20 ℃, and the protective gas is Ar or N 2 。
9. The method for preparing the spherical powder of the refractory entropy control material for additive manufacturing according to claim 1, wherein the specific operation in the third step is as follows: placing the spray-dried powder into a vacuum furnace, and introducing protective gas Ar or N 2 Then the temperature is raised from room temperature to T at 10 ℃ per minute 1 Temperature at T 1 Preserving heat for 1-4 h at the temperature, then from T 1 The temperature is raised to T at 5 ℃/min 2 Temperature at T 2 Preserving heat for 2-6 h at the temperature, and then cooling to room temperature along with a furnace, wherein the T is 1 The temperature range is 400-600 ℃, T 2 The temperature range is 1000-1400 ℃.
10. The method for preparing spherical powder of refractory entropy control material for additive manufacturing of claim 1, wherein the fourth step of plasma spheroidization control conditions are: the running power of the equipment is 10-85 kW, the flow rate of argon is 30-200 slpm, the flow rate of hydrogen is 2-20 slpm, and the powder feeding rate is 10-60 g/min.
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