CN113798504B - Preparation method of rare earth oxide dispersion-reinforced tungsten powder for 3D printing - Google Patents
Preparation method of rare earth oxide dispersion-reinforced tungsten powder for 3D printing Download PDFInfo
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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
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
- B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
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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
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
- C22C27/04—Alloys based on tungsten or molybdenum
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/001—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
- C22C32/0015—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides with only single oxides as main non-metallic constituents
- C22C32/0031—Matrix based on refractory metals, W, Mo, Nb, Hf, Ta, Zr, Ti, V or alloys thereof
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
Abstract
The preparation method of the rare earth oxide dispersion strengthening tungsten powder for 3D printing comprises the following steps: (1) Mixing ammonium metatungstate and rare earth nitrate according to a set proportion to form a solid mixture; (2) preparing a raw material solution by the solid mixture and water; (3) Adding the raw material solution into a mixed solution of ammonia water and ethanol to obtain ammonium metatungstate and rare earth hydroxide precipitate; (4) Drying the ammonium metatungstate and rare earth hydroxide precipitate at a first temperature to obtain ammonium metatungstate-rare earth hydroxide mixture powder; (5) Calcining the ammonium metatungstate-rare earth hydroxide mixture powder at a second temperature to obtain tungsten oxide-rare earth oxide mixture powder; (6) Adding seed crystals into the tungsten oxide-rare earth oxide mixed powder for mixing, and continuously reducing at a third temperature and a fourth temperature in a hydrogen atmosphere in sequence to obtain large-particle rare earth oxide dispersion-enhanced tungsten powder; (7) And (3) performing sphericizing treatment to obtain spherical rare earth oxide dispersion-enhanced tungsten powder.
Description
Technical Field
The application belongs to the technical field of 3D printing, in particular to the technical field of additive manufacturing, and particularly relates to a preparation method of rare earth oxide dispersion-reinforced tungsten powder for 3D printing.
Background
Tungsten is a representative refractory metal and has many excellent properties such as high melting point, good wear resistance, good corrosion resistance, high thermal conductivity and the like. Based on these excellent properties, tungsten-based materials have been widely used in the aerospace, medical and nuclear industries. However, tungsten has poor workability due to its high ductile-brittle transition temperature (200-400 ℃), and tungsten parts are generally produced by powder metallurgy and powder injection molding methods. However, the above-described method has a limitation in producing a part having a complicated structure.
In recent years, the additive manufacturing can manufacture complex structural parts which are difficult or impossible to process by the traditional process without the traditional cutters or dies, and can greatly simplify the working procedures, reduce the manufacturing cost and shorten the manufacturing time, thereby showing great advantages in the aspect of manufacturing tungsten complex parts. However, tungsten with a high melting point shows high surface tension and high internal energy during additive manufacturing, resulting in the appearance of liquid tungsten balling, while the presence of impurities in tungsten also affects the grain boundary strength of tungsten, resulting in cracking, so far it has not been possible to obtain fully dense and crack-free tungsten parts by additive manufacturing, resulting in limited application of 3D printed produced tungsten parts.
Aiming at the problem of tungsten in 3D printing, researchers dope rare earth oxide into tungsten to play a role of dispersion strengthening and effectively improve the mechanical property of the alloy. Oxide particles are dispersed in the tungsten grains, and dislocation is inhibited and accumulated in the grains, so that the mechanical properties of tungsten are improved. In addition, the oxide particles are dispersed at the grain boundary, so that migration of the grain boundary can be blocked, growth of grains is inhibited, and grain refinement is promoted. The uniformity of rare earth oxide dispersion affects the performance of tungsten-based materials to a great extent, however, the conventional ball milling method is difficult to realize uniform dispersion of tungsten oxide particles on a microscopic scale, and the produced powder has irregular shape, poor flowability and low bulk density. The particles of the rare earth oxide doped tungsten powder prepared by the liquid phase chemical method are generally nano or submicron in size, and the particle size is too small. In summary, the powder produced by the conventional method is difficult to meet the requirement of 3D printing in powder performance, shape and particle size distribution, and it is particularly important to develop a preparation technology of high-performance rare earth oxide dispersion-reinforced tungsten powder for 3D printing.
Disclosure of Invention
In view of this, some embodiments disclose a method for preparing rare earth oxide dispersion-enhanced tungsten powder for 3D printing, the method comprising the steps of:
(1) Mixing ammonium metatungstate and rare earth nitrate according to a set proportion to form a solid mixture;
(2) Preparing a raw material solution by the solid mixture and water;
(3) Mixing ammonia water and ethanol to obtain a mixed solution, and adding the raw material solution into the mixed solution to obtain ammonium metatungstate and rare earth hydroxide precipitate;
(4) Drying the ammonium metatungstate and rare earth hydroxide precipitate at a first temperature to obtain ammonium metatungstate-rare earth hydroxide mixture powder;
(5) Calcining the ammonium metatungstate-rare earth hydroxide mixture powder at a second temperature to obtain tungsten oxide-rare earth oxide mixture powder;
(6) Continuously reducing the tungsten oxide-rare earth oxide mixed powder at a third temperature and a fourth temperature in sequence in a hydrogen atmosphere to obtain large-particle rare earth oxide dispersion-reinforced tungsten powder;
(7) Performing sphericizing treatment on the large-particle rare earth oxide dispersion-reinforced tungsten powder to obtain spherical rare earth oxide dispersion-reinforced tungsten powder; the sphericizing rate of the spherical rare earth oxide dispersion reinforced tungsten powder is not less than 95%, the Hall fluidity is not less than 6.5s/50g, and the apparent density is more than 9.0g/cm 3 The particle size distribution is between 15 and 53 mu m.
Further, the method for preparing rare earth oxide dispersion-strengthened tungsten powder for 3D printing disclosed in some embodiments, in step (6), further includes a step of adding seed crystals into the tungsten oxide-rare earth oxide mixed powder; the seed crystal is small-particle tungsten powder or small-particle rare earth oxide dispersion reinforced tungsten powder.
In the preparation method of the rare earth oxide dispersion strengthening tungsten powder for 3D printing disclosed in some embodiments, in the step (1), the mass ratio of ammonium metatungstate to rare earth nitrate is 10-50:1.
In the preparation method of the rare earth oxide dispersion strengthening tungsten powder for 3D printing disclosed in some embodiments, in the step (2), the mass ratio of the solid mixture to water is 1-3:1.
In the preparation method of the rare earth oxide dispersion strengthening tungsten powder for 3D printing disclosed in some embodiments, in the step (4), the first temperature is 50-80 ℃, and the drying time is 10-12 hours.
In the preparation method of the rare earth oxide dispersion strengthening tungsten powder for 3D printing disclosed in some embodiments, in the step (5), the second temperature is 400-600 ℃, and the calcination time is 2-4 hours.
In the preparation method of rare earth oxide dispersion-reinforced tungsten powder for 3D printing disclosed in some embodiments, in the step (5), calcination is performed in flowing air or argon.
In the preparation method of the rare earth oxide dispersion strengthening tungsten powder for 3D printing disclosed in some embodiments, in the step (6), the third temperature is 600 ℃, the reduction time is 1h at the third temperature, the fourth temperature is 800-1000 ℃, and the reduction time is 3-6 h at the fourth temperature.
In the preparation method of the rare earth oxide dispersion-reinforced tungsten powder for 3D printing disclosed in some embodiments, in the step (7), sphericizing treatment of the large-particle rare earth oxide dispersion-reinforced tungsten powder is performed in a radio frequency induction plasma spheroidizing device, wherein the power of a power supply is set to be 40-70 kW, and the flow rate of carrier gas is 4-20 L.min -1 The powder feeding rate is 20-70 g.min -1 The pressure of the reaction chamber is 20-50 kPa.
The embodiment discloses a preparation method of rare earth oxide dispersion strengthening tungsten powder for 3D printing, wherein in the step (3), the mass concentration of ammonia water is 15-25%.
The preparation method of the rare earth oxide dispersion strengthening tungsten powder for 3D printing disclosed by the embodiment of the application can obtain the large-particle spherical rare earth oxide dispersion strengthening tungsten powder, has high sphericity, narrow particle size distribution and ideal fluidity and loose packing density, and is an excellent raw material for 3D printing.
Drawings
FIG. 1 example 1 morphology map of large particle spheroidized rare earth oxide dispersion-enhanced tungsten powder
Detailed Description
The word "embodiment" as used herein does not necessarily mean that any embodiment described as "exemplary" is preferred or advantageous over other embodiments. Performance index testing in the examples of the present application, unless otherwise specified, was performed using conventional testing methods in the art. It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the disclosure.
Unless otherwise defined, technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs; other test methods and techniques not specifically mentioned in the present application are those commonly used by those skilled in the art.
The terms "substantially" and "about" are used herein to describe small fluctuations. For example, they may refer to less than or equal to ±5%, such as less than or equal to ±2%, such as less than or equal to ±1%, such as less than or equal to ±0.5%, such as less than or equal to ±0.2%, such as less than or equal to ±0.1%, such as less than or equal to ±0.05%. Numerical data presented or represented herein in a range format is used only for convenience and brevity and should therefore be interpreted flexibly to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range. For example, a numerical range of "1 to 5%" should be interpreted to include not only the explicitly recited values of 1% to 5%, but also include individual values and sub-ranges within the indicated range. Thus, individual values, such as 2%, 3.5% and 4%, and subranges, such as 1% to 3%, 2% to 4% and 3% to 5%, etc., are included in this numerical range. The same principle applies to ranges reciting only one numerical value. Moreover, such an interpretation applies regardless of the breadth of the range or the characteristics being described.
In this document, including the claims, conjunctions such as "comprising," including, "" carrying, "" having, "" containing, "" involving, "" containing, "and the like are to be construed as open-ended, i.e., to mean" including, but not limited to. The conjunctions "consisting of … …" and "consisting of … …" are closed conjunctions.
Numerous specific details are set forth in the following examples in order to provide a better understanding of the present application. It will be understood by those skilled in the art that the present application may be practiced without some of these specific details. In the examples, some methods, means, instruments, devices, etc. well known to those skilled in the art are not described in detail in order to highlight the gist of the present application.
On the premise of no conflict, the technical features disclosed by the embodiment of the application can be combined at will, and the obtained technical scheme belongs to the disclosure of the embodiment of the application.
In some embodiments, the method for preparing rare earth oxide dispersion-strengthened tungsten powder for 3D printing comprises the steps of:
(1) Mixing ammonium metatungstate and rare earth nitrate according to a set proportion to form a solid mixture; the ammonium metatungstate is used as a raw material source of tungsten element in the product, the rare earth nitrate is used as a raw material source of rare earth element in the product, the proportion of the ammonium metatungstate to the rare earth nitrate is generally set according to the content of rare earth oxide in the product prepared as required, and generally, the mass ratio of the ammonium metatungstate to the rare earth nitrate is controlled between 10 and 50:1 so as to control the mass content of the rare earth oxide in the rare earth oxide dispersion-enhanced tungsten powder to be between 1 and 5 percent;
(2) Preparing a raw material solution by the solid mixture and water; typically, a solid mixture of ammonium metatungstate and rare earth nitrate is dissolved in water to form a raw material solution, wherein the rare earth nitrate comprises any one of lanthanum nitrate, yttrium nitrate or cerium nitrate; generally, controlling the mass ratio of the solid mixture to water to be 1-3:1, and controlling the particle size of the product powder by controlling the concentration of the solution; the solubility of ammonium metatungstate in water and ethanol is extremely large, when an ammonium metatungstate solution is dripped into ethanol, ammonium metatungstate can be separated out, and the larger the concentration of the ammonium metatungstate solution is, the larger the precipitated particles are;
(3) Mixing ammonia water and ethanol to obtain a mixed solution, and adding the raw material solution into the mixed solution to obtain a mixed precipitate of ammonium metatungstate and rare earth hydroxide;
generally, after ammonia water and ethanol are mixed, uniform mixed solution is obtained, raw material solution is added into the mixed solution, rare earth nitrate reacts with the ammonia water to obtain rare earth hydroxide precipitate, meanwhile, ammonium metatungstate cannot be dissolved in the ethanol to be separated out as precipitate, and in the reaction process, rare earth hydroxide and ammonium metatungstate are simultaneously precipitated out to obtain a rare earth hydroxide-ammonium metatungstate mixed precipitate with uniform component distribution;
generally, the mass concentration of the ammonia water is 15-25%;
generally, in the process of adding the raw material solution into the mixed solution, the raw material solution is gradually added, and stirring is continuously carried out at the same time, so that the uniformity degree of the precipitation process is improved, the rare earth hydroxide is uniformly dispersed in the ammonium metatungstate, and the rare earth oxide is uniformly dispersed in tungsten powder particles in the later process;
generally, ammonia water is also added into ethanol, and then raw material solution is added into the ethanol, so that the process of adding the raw material solution into the mixed solution is realized; continuously stirring in the adding process to ensure that the materials are fully and uniformly mixed;
(4) Drying the mixed precipitate of ammonium metatungstate and rare earth hydroxide at a first temperature to obtain ammonium metatungstate-rare earth hydroxide mixture powder; generally, ammonium meta-tungstate and rare earth hydroxide precipitates are required to be washed and washed, then dried, the purity of the precipitates is improved, for example, ethanol is used for washing 2-3 times, and then the washed precipitates are heated to a first temperature for drying; drying is usually carried out in an oven, for example, the temperature of the oven is controlled to be 50-80 ℃, and then the temperature is kept for a certain time to obtain dried ammonium metatungstate-rare earth hydroxide mixture powder;
generally, the drying time is controlled to be 10-12 hours;
(5) Calcining the ammonium metatungstate-rare earth hydroxide mixture powder at a second temperature to obtain tungsten oxide-rare earth oxide mixture powder; calcining the dried ammonium metatungstate-rare earth hydroxide mixture powder, wherein the ammonium metatungstate is converted into tungsten oxide, the rare earth hydroxide is converted into rare earth oxide, and the obtained product is tungsten oxide-rare earth oxide mixed powder, wherein the second temperature of calcination is controlled to be 400-600 ℃ and the calcination time is controlled to be 2-4 h;
typically, calcination is carried out in flowing air or argon; the yellow tungsten oxide is obtained by calcination in flowing air atmosphere, the blue tungsten oxide is obtained by calcination in argon atmosphere due to oxygen deficiency, the reduction activity of the blue tungsten oxide is good, and the granularity is easier to control.
(6) Continuously reducing the tungsten oxide-rare earth oxide mixed powder at a third temperature and a fourth temperature in sequence in a hydrogen atmosphere to obtain large-particle rare earth oxide dispersion-reinforced tungsten powder; generally, the tungsten oxide-rare earth oxide mixed powder is reduced in hydrogen atmosphere to obtain rare earth oxide doped tungsten powder particles, but the obtained product particles are fine, and the fine rare earth oxide doped tungsten powder particles are not beneficial to sphericizing particles in the later process, therefore, as an alternative embodiment, the inventor adds seed crystals into the tungsten oxide-rare earth oxide mixed powder, then the seed crystals are mixed with the tungsten oxide-rare earth oxide mixed powder to participate in a reduction reaction, and technological parameters of the reduction process are changed to promote the formation of large-particle rare earth oxide dispersion reinforced tungsten powder with the diameter of more than 5 mu m in the reduction process; for example, small-particle tungsten powder is used as seed crystal, vapor and tungsten powder directly react at high temperature to produce gaseous tungsten oxide hydrate, the tungsten oxide hydrate is further reduced into tungsten powder in hydrogen and deposited on the surfaces of the tungsten powder seed crystal particles, so that the particle size of the tungsten powder particles is increased, and meanwhile, the tungsten powder particles can mutually gather and recrystallize at high temperature and can promote the particle size of the tungsten powder to be increased; as an alternative embodiment, small-particle rare earth oxide dispersion-strengthened tungsten powder is used as seed crystal and added into the tungsten oxide-rare earth oxide mixed powder.
In general, in the prepared large-particle rare earth oxide dispersion-strengthening tungsten powder, a certain distribution range exists for particle size, in order to further control the particle size of a product to be more uniform and have a narrower distribution range, the large-particle rare earth oxide dispersion-strengthening tungsten powder product is screened, and the rare earth oxide dispersion-strengthening tungsten powder with overlarge particle size and overlarge particle size is removed to obtain the large-particle rare earth oxide dispersion-strengthening tungsten powder with a narrower particle size distribution range; as an alternative embodiment, the screened small-particle rare earth oxide dispersion-strengthened tungsten powder is used as seed crystal to be mixed with tungsten oxide-rare earth oxide mixed powder to participate in the reduction process in hydrogen atmosphere; on the one hand, the volatilization-deposition growth of tungsten powder is that oxide volatilizes and vapor forms gaseous oxide hydrate at high temperature, and the gaseous oxide hydrate is reduced into metal tungsten by hydrogen in gas phase to be deposited on the surface of the tungsten powder, so that the particle size of tungsten powder particles is increased; on the other hand, the oxidation-reduction growth of the tungsten powder is carried out, the tungsten powder is oxidized by water vapor at high temperature and then reduced by hydrogen, and the tungsten powder is repeatedly grown. Meanwhile, tungsten powder particles can mutually gather and recrystallize at high temperature, and the particle size of tungsten powder can be promoted to be increased;
generally, the third temperature is 600 ℃, the reduction time is 1h at the third temperature, tungsten trioxide can be completely converted into tungsten dioxide, then the temperature is continuously increased to the fourth temperature of 800-1000 ℃, the reduction time is 3-6 h at the fourth temperature, tungsten dioxide can be converted into metal tungsten, and large-particle rare earth oxide dispersion-enhanced tungsten powder is obtained;
generally, by controlling the dew point of the hydrogen in the reducing atmosphere to be 10-30 ℃, the higher the dew point of the hydrogen is, the better the volatilization deposition and oxidation reduction growth effects of the tungsten powder are, the larger the particle size of the rare earth oxide dispersion-strengthening tungsten powder is, the flow rate and the heat preservation time of the hydrogen are controlled, the particle size of the rare earth oxide dispersion-strengthening tungsten powder is also controlled, and generally, the smaller the flow rate of the hydrogen is, the longer the reduction time is, and the larger the particle size of the tungsten powder is. Generally, too large hydrogen flow can take away too much vapor generated in the reduction process, so that partial pressure of the vapor in the furnace is reduced, which is unfavorable for growth of tungsten powder, so that the hydrogen flow is usually controlled in a smaller range, and the particle size growth of tungsten powder is promoted. Generally, the reduction time is prolonged, which is favorable for aggregation and recrystallization of tungsten powder and for growth of tungsten powder, so that the reduction time is controlled in a longer range, and the particle size growth of tungsten powder is promoted.
(7) Performing sphericizing treatment on the large-particle rare earth oxide dispersion-reinforced tungsten powder to obtain spherical rare earth oxide dispersion-reinforced tungsten powder; the sphericizing rate of the spherical rare earth oxide dispersion reinforced tungsten powder is not less than 95%, the Hall fluidity is not less than 6.5s/50g, and the apparent density is more than 9.0g/cm 3 The particle size distribution is between 15 and 53 mu m. The spheroidizing treatment of the large-particle rare earth oxide dispersion-reinforced tungsten powder is usually carried out in a spheroidizing device, for example, a radio frequency induction plasma spheroidizing device, wherein the power of a power supply is set to be 40-70 kW, and the flow rate of carrier gas is 4-W20L·min -1 The powder feeding rate is 20-70 g.min -1 The pressure of the reaction chamber is 20-50 kPa.
The radio frequency induction plasma spheroidizing device comprises a plasma torch, a power supply unit, a powder supply system, a gas conveying system, a cooling chamber and a powder collector, wherein the side gas and the center gas used by the radio frequency induction plasma spheroidizing device are argon, and the carrier gas is argon or hydrogen.
Example 1
Lanthanum oxide La 2 O 3 Preparation of lanthanum oxide dispersion-reinforced tungsten powder with mass content of 1%
The preparation method of the rare earth oxide dispersion strengthening tungsten powder for 3D printing disclosed in the embodiment 1 comprises the following steps:
(1) 100g of ammonium metatungstate and 2.3g of lanthanum nitrate hexahydrate are mixed into a solid mixture;
(2) Adding the solid mixture into 100ml of deionized water, stirring and dissolving to prepare a raw material solution;
(3) Mixing 5ml of ammonia water with the mass content of 25% with ethanol to obtain a mixed solution, adding the raw material solution into the mixed solution, and continuously stirring until ammonium metatungstate and rare earth hydroxide precipitate are obtained;
(4) Washing the ammonium metatungstate and rare earth hydroxide precipitate with ethanol for three times, and drying at a first temperature of 60 ℃ for 12 hours to obtain ammonium metatungstate-lanthanum hydroxide mixture powder;
(5) Calcining the ammonium metatungstate-lanthanum hydroxide mixture powder at the second temperature of 550 ℃ for 2 hours to obtain tungsten oxide-lanthanum oxide mixture powder;
(6) Adding seed crystal fine tungsten into the tungsten oxide-lanthanum oxide mixed powder, mixing, and carrying out 200 mL-min -1 Sequentially reducing in hydrogen flow at a third temperature of 600 ℃ for 2h and a fourth temperature of 850 ℃ for 2h, and cooling along with a furnace after the reduction is finished to obtain a large-particle lanthanum oxide dispersion-reinforced tungsten powder product; screening the large-particle lanthanum oxide dispersion-reinforced tungsten powder product, and screening out particles with overlarge particle size and overlarge particle size to obtain the large-particle lanthanum oxide dispersion-reinforced tungsten powder product with narrower distribution;
(7) Large-particle lanthanum oxide dispersion-reinforced tungsten powder in radio frequency induction plasmaThe sphericizing treatment is carried out in a sphericizing device, the power supply power is regulated to 60kW, and the flow rate of carrier gas Ar is 8 L.min -1 The Ar flow of the side gas is 150 L.min -1 The Ar flow of the central gas is 15 L.min -1 Powder feeding rate is 45 g.min -1 The pressure of the reaction chamber is 30kPa, so as to obtain spherical lanthanum oxide dispersion-reinforced tungsten powder; lanthanum oxide dispersion-strengthened tungsten powder may also be commonly referred to as W-La 2 O 3 Alloy powder;
the performance of the obtained spherical lanthanum oxide dispersion-strengthened tungsten powder is detected, the morphology of the spherical lanthanum oxide dispersion-strengthened tungsten powder is shown in a large-particle spherical rare earth oxide dispersion-strengthened tungsten powder morphology chart of the embodiment 1 in the figure 1, and the scanning electron microscope chart shows that the sphericity is 96%, the sphericity is high, the particle size distribution is narrow, and D 50 28 μm, a Hall flowability of 6.28s/50g, a bulk density of 9.15g/cm 3 。
Example 2
Lanthanum oxide La 2 O 3 Preparation of lanthanum oxide dispersion-enhanced tungsten powder with mass content of 1%
The preparation method of rare earth oxide dispersion strengthening tungsten powder for 3D printing disclosed in the embodiment 2 comprises the following steps:
(1) 200g of ammonium metatungstate and 4.6g of lanthanum nitrate hexahydrate are mixed into a solid mixture;
(2) Adding the solid mixture into 100ml of deionized water, stirring and dissolving to prepare a raw material solution;
(3) 10ml of ammonia water with mass content of 25% is mixed with ethanol to obtain mixed solution, and the raw material solution is added into the mixed solution and is continuously stirred until ammonium metatungstate and rare earth hydroxide precipitate are obtained;
(4) Washing the ammonium metatungstate and rare earth hydroxide precipitate with ethanol for three times, and drying at a first temperature of 60 ℃ for 12 hours to obtain ammonium metatungstate-lanthanum hydroxide mixture powder;
(5) Calcining the ammonium metatungstate-lanthanum hydroxide mixture powder at the second temperature of 550 ℃ for 2 hours to obtain tungsten oxide-lanthanum oxide mixture powder;
(6) Adding seed fine particles of lanthanum oxide dispersion-strengthened tungsten powder (lanthanum oxide dispersion-strengthened tungsten powder with too small particle size obtained in example 1) to the mixed tungsten oxide-lanthanum oxide powder, mixing, and stirring150mL·min -1 Sequentially reducing in hydrogen flow at a third temperature of 600 ℃ for 2h and a fourth temperature of 1000 ℃ for 4h, and cooling along with a furnace after the reduction is finished to obtain large-particle lanthanum oxide dispersion-reinforced tungsten powder;
(7) Performing sphericizing treatment on large-particle lanthanum oxide dispersion-reinforced tungsten powder in a radio frequency induction plasma sphericizing device, adjusting the power supply power to 60kW and regulating the Ar carrier gas flow to 6 L.min -1 Ar side air flow rate is 150 L.min -1 Ar center gas flow rate 15 L.min -1 Powder feeding rate is 30 g.min -1 The pressure of the reaction chamber is 30kPa, so as to obtain spherical lanthanum oxide dispersion-reinforced tungsten powder;
the performance of the obtained spherical lanthanum oxide dispersion-reinforced tungsten powder is detected, the sphericity rate is 99%, the sphericity is high, the particle size distribution is narrow, and D 50 35 μm, a Hall flowability of 6.10s/50g, a bulk density of 9.36g/cm 3 。
Example 3
Lanthanum oxide La 2 O 3 Preparation of lanthanum oxide dispersion-enhanced tungsten powder with mass content of 1%
The preparation method of rare earth oxide dispersion strengthening tungsten powder for 3D printing disclosed in the embodiment 3 comprises the following steps:
(1) 200g of ammonium metatungstate and 4.6g of lanthanum nitrate hexahydrate are mixed into a solid mixture;
(2) Adding the solid mixture into 100ml of deionized water, stirring and dissolving to prepare a raw material solution;
(3) 10ml of ammonia water with mass content of 25% is mixed with ethanol to obtain mixed solution, and the raw material solution is added into the mixed solution and is continuously stirred until ammonium metatungstate and rare earth hydroxide precipitate are obtained;
(4) Washing the ammonium metatungstate and rare earth hydroxide precipitate with ethanol for three times, and drying at a first temperature of 60 ℃ for 12 hours to obtain ammonium metatungstate-lanthanum hydroxide mixture powder;
(5) Calcining the ammonium metatungstate-lanthanum hydroxide mixture powder at the second temperature of 550 ℃ for 2 hours to obtain tungsten oxide-lanthanum oxide mixture powder;
(6) The mixed powder of tungsten oxide and lanthanum oxide is 150 mL/min -1 In the hydrogen stream at a third temperature of 6Reducing for 2h at 00 ℃ and reducing for 4h at a fourth temperature of 1000 ℃, and cooling along with a furnace after the reduction is finished to obtain large-particle lanthanum oxide dispersion-reinforced tungsten powder;
(7) Performing sphericizing treatment on large-particle lanthanum oxide dispersion-reinforced tungsten powder in a radio frequency induction plasma sphericizing device, adjusting the power supply power to 60kW and regulating the Ar carrier gas flow to 6 L.min -1 Ar side air flow rate is 150 L.min -1 Ar center gas flow rate 15 L.min -1 Powder feeding rate is 30 g.min -1 The pressure of the reaction chamber is 30kPa, so as to obtain spherical lanthanum oxide dispersion-reinforced tungsten powder;
the performance of the obtained spherical lanthanum oxide dispersion-reinforced tungsten powder is detected, the sphericity rate is 99%, the sphericity is high, the particle size distribution is narrow, and D 50 32 μm, a Hall flowability of 6.22s/50g, a bulk density of 9.21g/cm 3 。
The preparation method of the rare earth oxide dispersion strengthening tungsten powder for 3D printing disclosed by the embodiment of the application can obtain the large-particle spherical rare earth oxide dispersion strengthening tungsten powder, has high sphericity, narrow particle size distribution and ideal fluidity and loose packing density, and is an excellent raw material for 3D printing.
The technical details disclosed in the technical scheme and the embodiment of the application are only illustrative of the inventive concept of the application and are not limiting to the technical scheme of the application, and all the technical details disclosed in the application have the same inventive concept as the application, and are within the protection scope of the claims of the application.
Claims (2)
- The preparation method of the rare earth oxide dispersion strengthening tungsten powder for 3D printing is characterized by comprising the following steps:(1) Mixing ammonium metatungstate and rare earth nitrate according to a set proportion to form a solid mixture; wherein the mass ratio of the ammonium metatungstate to the rare earth nitrate is 10-50:1;(2) Preparing a raw material solution by the solid mixture and water; wherein the mass ratio of the solid mixture to water is 1-3:1;(3) Mixing ammonia water and ethanol to obtain a mixed solution, and adding the raw material solution into the mixed solution to obtain ammonium metatungstate and rare earth hydroxide precipitate; wherein the mass concentration of the ammonia water is 15-25%;(4) Drying the ammonium metatungstate and rare earth hydroxide precipitate at a first temperature to obtain ammonium metatungstate-rare earth hydroxide mixture powder; wherein the first temperature is 50-80 ℃ and the drying time is 10-12 h;(5) Calcining the ammonium metatungstate-rare earth hydroxide mixture powder at a second temperature to obtain tungsten oxide-rare earth oxide mixture powder; wherein the second temperature is 400-600 ℃, and the calcination time is 2-4 h;(6) Adding seed crystals into the tungsten oxide-rare earth oxide mixed powder, and continuously reducing at a third temperature and a fourth temperature in a hydrogen atmosphere in sequence to obtain large-particle rare earth oxide dispersion-reinforced tungsten powder; the seed crystal is small-particle tungsten powder or small-particle rare earth oxide dispersion-reinforced tungsten powder, the third temperature is 600 ℃, the reduction time is 1h at the third temperature, the fourth temperature is 800-1000 ℃, and the reduction time is 3-6 h at the fourth temperature;(7) The large-particle rare earth oxide dispersion-strengthening tungsten powder is subjected to sphericizing treatment to obtain spherical rare earth oxide dispersion-strengthening tungsten powder; wherein, the sphericizing treatment of the large-particle rare earth oxide dispersion strengthening tungsten powder is carried out in a radio frequency induction plasma spheroidizing device, wherein, the power supply power is set to be 40-70 kW, and the carrier gas flow is 4-20L min -1 The powder feeding rate is 20-70 g min -1 The pressure of the reaction chamber is 20-50 kPa; the sphericizing rate of the spherical rare earth oxide dispersion strengthening tungsten powder is not less than 95%, the Hall fluidity is not less than 6.5s/50g, and the apparent density is more than 9.0g/cm 3 The particle size distribution is between 15 and 53 mu m.
- 2. The method for producing a rare earth oxide dispersion-strengthened tungsten powder for 3D printing according to claim 1, wherein in step (5), calcination is performed in flowing air or argon gas.
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