CN113798504A - Preparation method of rare earth oxide dispersion-enhanced tungsten powder for 3D printing - Google Patents
Preparation method of rare earth oxide dispersion-enhanced tungsten powder for 3D printing Download PDFInfo
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- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
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- 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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- 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
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- C22C27/04—Alloys based on tungsten or molybdenum
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- 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
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Abstract
The preparation method of the rare earth oxide dispersion-enhanced tungsten powder for 3D printing comprises the following steps: (1) mixing ammonium metatungstate and rare earth nitrate according to a set proportion to obtain 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 precipitates; (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 mixed powder; (6) adding seed crystals into the tungsten oxide-rare earth oxide mixed powder, mixing, and continuously reducing at a third temperature and a fourth temperature in sequence in a hydrogen atmosphere to obtain large-particle rare earth oxide dispersion-enhanced tungsten powder; (7) and performing sphericizing treatment to obtain the spherical rare earth oxide dispersion-strengthened tungsten powder.
Description
Technical Field
The application belongs to the technical field of 3D printing, particularly belongs 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 a plurality of 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, since tungsten has a high ductile-brittle transition temperature (200-. However, the above 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 cutter or mould, can greatly simplify the process, reduce the manufacturing cost and shorten the manufacturing time, and has great advantages in manufacturing tungsten complex parts. However, tungsten with a high melting point exhibits high surface tension and high internal energy in the additive manufacturing process, which results in the occurrence of liquid tungsten balling, and the existence of impurities in tungsten also affects the grain boundary strength of tungsten, thereby causing cracking, so far, it is still impossible to obtain a fully dense and crack-free tungsten part through additive manufacturing, and the application of the tungsten part produced by 3D printing is limited.
Aiming at the problems of the tungsten in 3D printing, scientific researchers dope the rare earth oxide into the tungsten to play a role in dispersion strengthening and effectively improve the mechanical properties of the alloy. The oxide particles are dispersed in the tungsten crystal grains, and dislocation is inhibited and accumulated in the crystal grains, so that the mechanical property of the tungsten is improved. In addition, the oxide particles are dispersed at the grain boundary, so that the migration of the grain boundary can be hindered, the growth of the grains can be inhibited, and the grain refinement can be promoted. The uniformity of the dispersion of the rare earth oxide greatly affects the performance of the tungsten-based material, but 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 apparent 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 conclusion, the powder produced by the traditional method hardly meets the requirements of 3D printing in terms of powder performance, shape and particle size distribution, and the development of a preparation technology of the high-performance rare earth oxide dispersion-reinforced tungsten powder for 3D printing is particularly important.
Disclosure of Invention
In view of this, some embodiments disclose a method for preparing rare earth oxide dispersion-strengthened 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 obtain 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 a hydrogen atmosphere in sequence to obtain large-particle rare earth oxide dispersion-enhanced tungsten powder;
(7) carrying out spheroidization treatment on the large-particle rare earth oxide dispersion-strengthened tungsten powder to obtain spherical rare earth oxide dispersion-strengthened tungsten powder; the sphericizing rate of the spherical rare earth oxide dispersion reinforced tungsten powder is not less than 95 percent, the Hall fluidity is not less than 6.5s/50g, and the apparent density is more than 9.0g/cm3The particle size is 15-53 μm.
Further, some embodiments disclose the preparation method of the rare earth oxide dispersion-strengthened tungsten powder for 3D printing, in the step (6), further comprising a step of adding a seed crystal to 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.
Some embodiments disclose a preparation method of rare earth oxide dispersion-strengthened tungsten powder for 3D printing, wherein in the step (1), the mass ratio of ammonium metatungstate to rare earth nitrate is 10-50: 1.
Some embodiments disclose a preparation method of rare earth oxide dispersion-strengthened tungsten powder for 3D printing, wherein in the step (2), the mass ratio of the solid mixture to water is 1-3: 1.
Some embodiments disclose a preparation method of rare earth oxide dispersion-strengthened tungsten powder for 3D printing, wherein in the step (4), the first temperature is 50-80 ℃, and the drying time is 10-12 hours.
Some embodiments disclose the preparation method of the rare earth oxide dispersion-strengthened tungsten powder for 3D printing, wherein in the step (5), the second temperature is 400-600 ℃, and the calcination time is 2-4 hours.
Some examples disclose methods of preparing rare earth oxide dispersion-strengthened tungsten powder for 3D printing, wherein in step (5), the calcination is performed in flowing air or argon gas.
Some embodiments disclose the preparation method of the rare earth oxide dispersion-strengthened tungsten powder for 3D printing, in the step (6), the third temperature is 600 ℃, the reduction time is 1 hour at the third temperature, the fourth temperature is 800-1000 ℃, and the reduction time is 3-6 hours at the fourth temperature.
Some embodiments disclose a preparation method of rare earth oxide dispersion-enhanced tungsten powder for 3D printing, in the step (7), the spheroidization of the large-particle rare earth oxide dispersion-enhanced tungsten powder is performed in a radio frequency induction plasma spheroidization device, wherein the power supply is set to 40-70 kW, and the carrier gas flow is 4-20 l.min-1The powder feeding rate is 20-70 g.min-1The pressure in the reaction chamber is 20 to 50 kPa.
Some embodiments disclose the preparation method of the rare earth oxide dispersion-strengthened 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-strengthened tungsten powder for 3D printing, disclosed by the embodiment of the application, can be used for obtaining the large-particle spheroidized rare earth oxide dispersion-strengthened tungsten powder, is high in spheroidization rate and narrow in particle size distribution, has ideal fluidity and apparent density, and is an excellent raw material for 3D printing.
Drawings
FIG. 1 example 1 is a morphology chart of large-particle spheroidized rare earth oxide dispersion-strengthened tungsten powder
Detailed Description
The word "embodiment" as used herein, is not necessarily to be construed as preferred or advantageous over other embodiments, including any embodiment illustrated as "exemplary". Performance index tests in the examples of this application, unless otherwise indicated, were performed using routine experimentation 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 defined otherwise, 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 employed by those of ordinary skill in the art.
The terms "substantially" and "about" are used herein to describe small fluctuations. For example, they may mean 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 represented or presented herein in a range format is used merely for convenience and brevity and thus should 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 as if each numerical value and sub-range is explicitly recited. 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, included in this numerical range are individual values, such as 2%, 3.5%, and 4%, and sub-ranges, such as 1% to 3%, 2% to 4%, and 3% to 5%, etc. This principle applies equally 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 understood to be open-ended, i.e., to mean" including but not limited to. The conjunctions "consisting of … …" and "consisting of … …" are closed conjunctions.
In the following detailed description, numerous specific details are set forth in order to provide a better understanding of the present disclosure. 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, apparatuses, etc. known to those skilled in the art are not described in detail in order to highlight the subject matter of the present application.
On the premise of no conflict, the technical features disclosed in the embodiments of the present application may be combined arbitrarily, and the obtained technical solution belongs to the content disclosed in the embodiments of the present application.
In some embodiments, a method for preparing a rare earth oxide dispersion-reinforced tungsten powder for 3D printing includes the steps of:
(1) mixing ammonium metatungstate and rare earth nitrate according to a set proportion to obtain a solid mixture; ammonium metatungstate is used as a raw material source of tungsten element in the product, rare earth nitrate is used as a raw material source of rare earth element in the product, the proportion of ammonium metatungstate and rare earth nitrate is generally set according to the content of rare earth oxide in the product to be prepared, generally, the mass ratio of ammonium metatungstate to rare earth nitrate is controlled to be 10-50: 1 so as to control the mass content of rare earth oxide in the rare earth oxide dispersion reinforced tungsten powder to be 1-5%;
(2) preparing a raw material solution by the solid mixture and water; generally, 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, the mass ratio of the solid mixture to water is controlled to be 1-3: 1, and the particle size of the product powder is controlled by controlling the concentration of the solution; generally, the solubility difference of ammonium metatungstate in water and ethanol is very large, when the ammonium metatungstate solution is dropwise added into ethanol, ammonium metatungstate can be separated out, and the larger the concentration of the ammonium metatungstate solution is, the larger the separated 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 liquor is obtained, a raw material solution is added into the mixed liquor, rare earth nitrate reacts with the ammonia water to obtain rare earth hydroxide precipitate, meanwhile, ammonium metatungstate cannot be dissolved in the ethanol and precipitates out as precipitate, and the rare earth hydroxide and the ammonium metatungstate precipitate out simultaneously in the reaction process to obtain a rare earth hydroxide-ammonium metatungstate mixed precipitate with uniform component distribution;
generally, the mass concentration of 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 meanwhile, the stirring is continuously carried out, so that the uniformity degree in the precipitation process is improved, the rare earth hydroxide is uniformly dispersed in the ammonium metatungstate, and the uniform dispersion distribution of the rare earth oxide in the tungsten powder particles in the later process is facilitated;
generally, ammonia water is added into ethanol, and then the 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 fully and uniformly mix;
(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 metatungstate and rare earth hydroxide precipitates need to be cleaned and washed, and then dried to improve the purity of the precipitates, for example, the precipitates are washed with ethanol for 2-3 times, and then the washed precipitates are heated to a first temperature for drying; usually, drying is carried out in an oven, for example, the temperature of the oven is controlled to be 50-80 ℃, and then heat preservation is carried out for a certain time to obtain dry ammonium metatungstate-rare earth hydroxide mixture powder;
generally, the drying time is controlled to be 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; 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, the obtained product is tungsten oxide-rare earth oxide mixed powder, the second temperature of the calcination is usually controlled to be 400-600 ℃, and the calcination time is 2-4 hours;
typically, calcination is carried out in flowing air or argon; the yellow tungsten oxide is obtained by calcining in a flowing air atmosphere, and the blue tungsten oxide is obtained by calcining in an argon atmosphere due to the lack of oxygen, so that the blue tungsten oxide has good reduction activity and the particle size is easier to control.
(6) Continuously reducing the tungsten oxide-rare earth oxide mixed powder 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; generally, tungsten oxide-rare earth oxide mixed powder is reduced in a 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 the spheroidization of the particles in the later process, therefore, as an optional 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 changes the process parameters of the reduction process to promote the reduction process to enhance the formation of the tungsten powder by dispersing the large-particle rare earth oxide with the particle size of more than 5 microns; for example, small-particle tungsten powder is used as a seed crystal, water vapor and tungsten powder directly react at high temperature to produce gaseous tungsten oxide hydrate, the tungsten oxide hydrate is further reduced to tungsten powder in hydrogen and deposited on the surface of the tungsten powder seed crystal particles, the particle size of the tungsten powder particles is increased, and meanwhile, the tungsten powder particles can be mutually aggregated and recrystallized at high temperature, and the particle size of the tungsten powder can also be increased; as an alternative example, small particle rare earth oxide dispersion strengthened tungsten powder is used as seed crystal and added into tungsten oxide-rare earth oxide mixed powder.
Generally, the particle size of the prepared large-particle rare earth oxide dispersion-enhanced tungsten powder has a certain distribution range, and in order to further control the particle size of the product to be more uniform and narrower, the large-particle rare earth oxide dispersion-enhanced tungsten powder product is screened to remove the rare earth oxide dispersion-enhanced tungsten powder with overlarge particle size and undersize particle size, so as to obtain the large-particle rare earth oxide dispersion-enhanced tungsten powder with narrower particle size distribution range; as an optional embodiment, the screened small-particle rare earth oxide dispersion reinforced tungsten powder is used as a seed crystal, mixed with tungsten oxide-rare earth oxide mixed powder and participated in the reduction process in hydrogen atmosphere; on one hand, the volatilization-deposition growth of the tungsten powder is carried out, the oxide volatilizes at high temperature to form gaseous oxide hydrate with water vapor, the gaseous oxide hydrate is reduced into metal tungsten by hydrogen in a gas phase to be deposited on the surface of the tungsten powder, and the particle size of tungsten powder particles is increased; on the other hand, the tungsten powder grows by oxidation-reduction, the tungsten powder is oxidized by water vapor at high temperature and then reduced by hydrogen, and the tungsten powder grows by repeating the steps. Meanwhile, tungsten powder particles can be mutually aggregated and recrystallized at high temperature, and the particle size of the tungsten powder can be increased;
generally, the third temperature is 600 ℃, the reduction time is 1 hour at the third temperature, the tungsten trioxide can be completely converted into the tungsten dioxide, then the temperature is continuously raised to the fourth temperature of 800-1000 ℃, the reduction time is 3-6 hours at the fourth temperature, the tungsten dioxide can be converted into the metal tungsten, and the large-particle rare earth oxide dispersion reinforced tungsten powder is obtained;
generally, by controlling the dew point of hydrogen in a reducing atmosphere to be 10-30 ℃, the higher the dew point of hydrogen is, the better the volatilization deposition and oxidation-reduction growth effects of tungsten powder are, the larger the particle size of rare earth oxide dispersion-enhanced tungsten powder is, the same the flow rate and heat preservation time of hydrogen are controlled, and the particle size of rare earth oxide dispersion-enhanced tungsten powder is also controlled, generally, the smaller the hydrogen flow rate is, the longer the reduction time is, and the larger the particle size of tungsten powder is. Generally, too much hydrogen flow can bring away too much water vapor generated in the reduction process, so that the partial pressure of the water vapor in the furnace is reduced, and the tungsten powder is not beneficial to growing, so the hydrogen flow is generally required to be controlled in a smaller range to promote the grain size of the tungsten powder to grow. Generally, the extension of the reduction time is beneficial to the aggregation and recrystallization of the tungsten powder and the growth of the tungsten powder, so the reduction time is generally controlled in a longer range to promote the growth of the particle size of the tungsten powder.
(7) Spheroidizing large-particle rare earth oxide dispersion-enhanced tungsten powderProcessing 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 percent, the Hall fluidity is not less than 6.5s/50g, and the apparent density is more than 9.0g/cm3The particle size is 15-53 μm. The spheroidization treatment of the large-particle rare earth oxide dispersion-enhanced tungsten powder is usually carried out in a spheroidization treatment device, such as a radio frequency induction plasma spheroidization device, wherein the power supply power is set to be 40-70 kW, and the carrier gas flow is 4-20 L.min-1The powder feeding rate is 20-70 g.min-1The pressure in the reaction chamber is 20 to 50 kPa.
The radio frequency induction plasma spheroidizing device generally comprises a plasma torch, a power supply unit, a powder supply system, a gas conveying system, a cooling chamber and a powder collector, wherein edge gas and central gas used by the radio frequency induction plasma spheroidizing device are argon, and carrier gas is argon or hydrogen.
Example 1
Lanthanum oxide La2O3Preparation of lanthanum oxide dispersion-reinforced tungsten powder with mass content of 1%
The preparation method of the rare earth oxide dispersion-strengthened tungsten powder for 3D printing disclosed in embodiment 1 includes the steps of:
(1)100g of ammonium metatungstate was mixed with 2.3g of lanthanum nitrate hexahydrate to form a solid mixture;
(2) adding the solid mixture into 100ml of deionized water, stirring and dissolving to prepare a raw material solution;
(3)5ml of 25% ammonia water and ethanol are mixed to obtain a mixed solution, the raw material solution is added into the mixed solution, and the mixture is continuously stirred until ammonium metatungstate and rare earth hydroxide precipitates are obtained;
(4) washing the ammonium metatungstate and rare earth hydroxide precipitate with ethanol for three times, and then 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 2h to obtain tungsten oxide-lanthanum oxide mixture powder;
(6) adding seed crystal fine particle tungsten into tungsten oxide-lanthanum oxide mixed powder, mixing,at 200 mL/min-1Reducing the hydrogen flow for 2 hours at a third temperature of 600 ℃ and reducing the hydrogen flow for 2 hours at a fourth temperature of 850 ℃ in sequence, and cooling the hydrogen flow along with the furnace after the reduction is finished to obtain a large-particle lanthanum oxide dispersion-enhanced tungsten powder product; screening the large-particle lanthanum oxide dispersion-strengthened tungsten powder product, and screening out particles with overlarge and undersize particle sizes to obtain a large-particle lanthanum oxide dispersion-strengthened tungsten powder product with narrow distribution;
(7) the large-particle lanthanum oxide dispersion-enhanced tungsten powder is subjected to spheroidization in a radio frequency induction plasma spheroidizing device, the power of a power supply is adjusted to be 60kW, and the flow of Ar of carrier gas is adjusted to be 8L-min-1Ar flow of the side gas is 150 L.min-1Central gas Ar flow rate 15L min-1Powder feeding rate of 45 g/min-1And the pressure of the reaction chamber is 30kPa to obtain spherical lanthanum oxide dispersion enhanced tungsten powder; lanthanum oxide dispersion strengthened tungsten powder can also be generally called W-La2O3Alloying powder;
the obtained spherical lanthanum oxide dispersion-strengthened tungsten powder is subjected to performance detection, the morphology of the tungsten powder is shown in the figure 1, the example 1 large-particle spheroidized rare earth oxide dispersion-strengthened tungsten powder morphology figure, the scanning electron microscope figure shows that the spheroidization rate is 96%, the sphericity is high, the particle size distribution is narrow, and D is50Has a particle size of 28 μm, a Hall flowability of 6.28s/50g, and a bulk density of 9.15g/cm3。
Example 2
Lanthanum oxide La2O3Preparation of lanthanum oxide dispersion-enhanced tungsten powder with mass content of 1%
The preparation method of the rare earth oxide dispersion-strengthened tungsten powder for 3D printing, disclosed in embodiment 2, comprises the steps of:
(1)200g of ammonium metatungstate was mixed with 4.6g of lanthanum nitrate hexahydrate to form a solid mixture;
(2) adding the solid mixture into 100ml of deionized water, stirring and dissolving to prepare a raw material solution;
(3) mixing 10ml of 25% ammonia water and 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 precipitates are obtained;
(4) washing the ammonium metatungstate and rare earth hydroxide precipitate with ethanol for three times, and then 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 2h to obtain tungsten oxide-lanthanum oxide mixture powder;
(6) seed crystal fine-particle lanthanum oxide dispersion-strengthened tungsten powder (lanthanum oxide dispersion-strengthened tungsten powder having an excessively small particle diameter obtained in example 1) was added to the tungsten oxide-lanthanum oxide mixed powder, and the mixture was mixed at 150 mL/min-1Reducing the hydrogen flow for 2 hours at a third temperature of 600 ℃ and reducing the hydrogen flow for 4 hours at a fourth temperature of 1000 ℃, and cooling the hydrogen flow along with the furnace after the reduction is finished to obtain large-particle lanthanum oxide dispersion-enhanced tungsten powder;
(7) the large-particle lanthanum oxide dispersion enhanced tungsten powder is subjected to spheroidization in a radio frequency induction plasma spheroidizing device, the power of a power supply is adjusted to be 60kW, and the flow of Ar carrier gas is adjusted to be 6 L.min-1Ar side gas flow rate of 150L/min-1Ar center gas flow rate of 15L min-1Powder feeding rate of 30 g/min-1And the pressure of the reaction chamber is 30kPa to obtain spherical lanthanum oxide dispersion enhanced tungsten powder;
the obtained spherical lanthanum oxide dispersion-strengthened tungsten powder is subjected to performance detection, the sphericization rate is 99%, the sphericity is high, the particle size distribution is narrow, and D5035 μm, a Hall flowability of 6.10s/50g, and a bulk density of 9.36g/cm3。
Example 3
Lanthanum oxide La2O3Preparation of lanthanum oxide dispersion-enhanced tungsten powder with mass content of 1%
The embodiment 3 discloses a preparation method of rare earth oxide dispersion-strengthened tungsten powder for 3D printing, which comprises the following steps:
(1)200g of ammonium metatungstate was mixed with 4.6g of lanthanum nitrate hexahydrate to form a solid mixture;
(2) adding the solid mixture into 100ml of deionized water, stirring and dissolving to prepare a raw material solution;
(3) mixing 10ml of 25% ammonia water and 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 precipitates are obtained;
(4) washing the ammonium metatungstate and rare earth hydroxide precipitate with ethanol for three times, and then 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 2h to obtain tungsten oxide-lanthanum oxide mixture powder;
(6) the tungsten oxide-lanthanum oxide mixed powder is 150 mL/min-1Reducing the hydrogen flow for 2 hours at a third temperature of 600 ℃ and reducing the hydrogen flow for 4 hours at a fourth temperature of 1000 ℃, and cooling the hydrogen flow along with the furnace after the reduction is finished to obtain large-particle lanthanum oxide dispersion-enhanced tungsten powder;
(7) the large-particle lanthanum oxide dispersion enhanced tungsten powder is subjected to spheroidization in a radio frequency induction plasma spheroidizing device, the power of a power supply is adjusted to be 60kW, and the flow of Ar carrier gas is adjusted to be 6 L.min-1Ar side gas flow rate of 150L/min-1Ar center gas flow rate of 15L min-1Powder feeding rate of 30 g/min-1And the pressure of the reaction chamber is 30kPa to obtain spherical lanthanum oxide dispersion enhanced tungsten powder;
the obtained spherical lanthanum oxide dispersion-strengthened tungsten powder is subjected to performance detection, the sphericization rate is 99%, the sphericity is high, the particle size distribution is narrow, and D5032 μm, a Hall flowability of 6.22s/50g, and a bulk density of 9.21g/cm3。
The preparation method of the rare earth oxide dispersion-strengthened tungsten powder for 3D printing, disclosed by the embodiment of the application, can be used for obtaining the large-particle spheroidized rare earth oxide dispersion-strengthened tungsten powder, is high in spheroidization rate and narrow in particle size distribution, has ideal fluidity and apparent density, and is an excellent raw material for 3D printing.
The technical solutions and the technical details disclosed in the embodiments of the present application are only examples to illustrate the inventive concept of the present application, and do not constitute limitations on the technical solutions of the present application, and all the inventive changes, substitutions, or combinations that are made to the technical details disclosed in the present application without creativity are the same as the inventive concept of the present application and are within the protection scope of the claims of the present application.
Claims (10)
- The preparation method of the rare earth oxide dispersion reinforced 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 obtain 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 precipitates;(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 mixed powder;(6) continuously reducing the tungsten oxide-rare earth oxide mixed powder 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) carrying out spheroidization treatment on the large-particle rare earth oxide dispersion-strengthened tungsten powder to obtain spherical rare earth oxide dispersion-strengthened 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/cm3The particle size is 15-53 μm.
- 2. The method for preparing rare earth oxide dispersion-strengthened tungsten powder for 3D printing according to claim 1, wherein the step (6) further comprises adding seed crystals to the tungsten oxide-rare earth oxide mixed powder, wherein the seed crystals are small-particle tungsten powder or small-particle rare earth oxide dispersion-strengthened tungsten powder.
- 3. The preparation method of the rare earth oxide dispersion-reinforced tungsten powder for 3D printing according to claim 1, wherein in the step (1), the mass ratio of the ammonium metatungstate to the rare earth nitrate is 10-50: 1.
- 4. The preparation method of the rare earth oxide dispersion-reinforced tungsten powder for 3D printing according to claim 1, wherein in the step (2), the mass ratio of the solid mixture to water is 1-3: 1.
- 5. The method for preparing rare earth oxide dispersion-strengthened tungsten powder for 3D printing according to claim 1, wherein in the step (4), the first temperature is 50-80 ℃ and the drying time is 10-12 h.
- 6. The method for preparing rare earth oxide dispersion-strengthened tungsten powder for 3D printing according to claim 1, wherein in the step (5), the second temperature is 400-600 ℃, and the calcination time is 2-4 h.
- 7. The method for preparing rare earth oxide dispersion-strengthened tungsten powder for 3D printing according to claim 1, wherein in the step (5), the calcination is performed in flowing air or argon gas.
- 8. The method for preparing rare earth oxide dispersion-strengthened tungsten powder for 3D printing according to claim 1, wherein 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.
- 9. The method for preparing rare earth oxide dispersion-strengthened tungsten powder for 3D printing according to claim 1, wherein in the step (7), the spheroidization of the large-particle rare earth oxide dispersion-strengthened tungsten powder is performed in a radio frequency induction plasma spheroidizing device, wherein the power supply is set to be 40-70 kW, and the carrier gas flow is 4-20L-min-1The powder feeding rate is 20-70 g.min-1The pressure in the reaction chamber is 20 to 50 kPa.
- 10. The preparation method of the rare earth oxide dispersion-reinforced tungsten powder for 3D printing according to claim 1, wherein in the step (3), the mass concentration of ammonia water is 15-25%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114713833A (en) * | 2022-03-10 | 2022-07-08 | 崇义章源钨业股份有限公司 | Spherical tungsten-based composite powder based on in-situ reduction and preparation method thereof |
| CN115533112A (en) * | 2022-10-17 | 2022-12-30 | 北京工业大学 | Method for refining refractory metals by composite rare earth tungsten/molybdate eutectic |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3234007A (en) * | 1963-02-27 | 1966-02-08 | Allied Chem | Reduction of tungsten hexafluoride to form improved tungsten particles |
| US3399981A (en) * | 1967-04-25 | 1968-09-03 | Allied Chem | Tungsten-rhenium alloys |
| US20040131538A1 (en) * | 2002-09-30 | 2004-07-08 | Fuji Photo Film Co., Ltd. | Method of producing metal particles, and metal oxide obtained from the particles |
| CN1569368A (en) * | 2004-05-10 | 2005-01-26 | 西安交通大学 | Method for preparing nm-class composite rare earth molybdenum material by sol-gal process |
| JP2013001985A (en) * | 2011-06-21 | 2013-01-07 | Sumitomo Metal Mining Co Ltd | Rare-earth transition metal-based alloy powder and method for producing the same |
| CN106001594A (en) * | 2016-07-15 | 2016-10-12 | 北京科技大学 | Preparation method for ultra-coarse spherical tungsten powder |
| US20170225234A1 (en) * | 2014-10-20 | 2017-08-10 | Central South University | A preparation method of rare earth oxide dispersion strengthened fine grain tungsten materials |
| CN110270692A (en) * | 2019-06-10 | 2019-09-24 | 北京科技大学 | A kind of tungsten/rare-earth oxide composite hollow spherical shape raw powder's production technology |
| CN110722171A (en) * | 2019-09-30 | 2020-01-24 | 北京科技大学 | Method for preparing rare earth oxide doped tungsten and molybdenum spherical powder for 3D printing |
| CN110983087A (en) * | 2019-12-28 | 2020-04-10 | 天津大学 | Method for improving oxide distribution in yttrium oxide dispersion strengthening tungsten alloy |
| CN111020333A (en) * | 2019-12-28 | 2020-04-17 | 天津大学 | Method for refining size of yttrium oxide at crystal boundary in yttrium oxide dispersion-strengthened tungsten-based alloy |
-
2021
- 2021-09-17 CN CN202111092226.5A patent/CN113798504B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3234007A (en) * | 1963-02-27 | 1966-02-08 | Allied Chem | Reduction of tungsten hexafluoride to form improved tungsten particles |
| US3399981A (en) * | 1967-04-25 | 1968-09-03 | Allied Chem | Tungsten-rhenium alloys |
| US20040131538A1 (en) * | 2002-09-30 | 2004-07-08 | Fuji Photo Film Co., Ltd. | Method of producing metal particles, and metal oxide obtained from the particles |
| CN1569368A (en) * | 2004-05-10 | 2005-01-26 | 西安交通大学 | Method for preparing nm-class composite rare earth molybdenum material by sol-gal process |
| JP2013001985A (en) * | 2011-06-21 | 2013-01-07 | Sumitomo Metal Mining Co Ltd | Rare-earth transition metal-based alloy powder and method for producing the same |
| US20170225234A1 (en) * | 2014-10-20 | 2017-08-10 | Central South University | A preparation method of rare earth oxide dispersion strengthened fine grain tungsten materials |
| CN106001594A (en) * | 2016-07-15 | 2016-10-12 | 北京科技大学 | Preparation method for ultra-coarse spherical tungsten powder |
| CN110270692A (en) * | 2019-06-10 | 2019-09-24 | 北京科技大学 | A kind of tungsten/rare-earth oxide composite hollow spherical shape raw powder's production technology |
| CN110722171A (en) * | 2019-09-30 | 2020-01-24 | 北京科技大学 | Method for preparing rare earth oxide doped tungsten and molybdenum spherical powder for 3D printing |
| CN110983087A (en) * | 2019-12-28 | 2020-04-10 | 天津大学 | Method for improving oxide distribution in yttrium oxide dispersion strengthening tungsten alloy |
| CN111020333A (en) * | 2019-12-28 | 2020-04-17 | 天津大学 | Method for refining size of yttrium oxide at crystal boundary in yttrium oxide dispersion-strengthened tungsten-based alloy |
Non-Patent Citations (1)
| Title |
|---|
| 游峰等: "喷雾干燥和一步氢还原制备超细钨粉工艺的研究", 中国钨业, vol. 23, no. 06, pages 15 - 18 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114713833A (en) * | 2022-03-10 | 2022-07-08 | 崇义章源钨业股份有限公司 | Spherical tungsten-based composite powder based on in-situ reduction and preparation method thereof |
| CN114713833B (en) * | 2022-03-10 | 2024-03-22 | 崇义章源钨业股份有限公司 | Spherical tungsten-based composite powder based on in-situ reduction and preparation method thereof |
| CN115533112A (en) * | 2022-10-17 | 2022-12-30 | 北京工业大学 | Method for refining refractory metals by composite rare earth tungsten/molybdate eutectic |
| CN115533112B (en) * | 2022-10-17 | 2023-10-20 | 北京工业大学 | Method for refining refractory metal by composite rare earth tungsten/molybdate eutectic |
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