CN109332717B - Preparation method of spherical molybdenum titanium zirconium alloy powder - Google Patents
Preparation method of spherical molybdenum titanium zirconium alloy powder Download PDFInfo
- Publication number
- CN109332717B CN109332717B CN201811101638.9A CN201811101638A CN109332717B CN 109332717 B CN109332717 B CN 109332717B CN 201811101638 A CN201811101638 A CN 201811101638A CN 109332717 B CN109332717 B CN 109332717B
- Authority
- CN
- China
- Prior art keywords
- powder
- alloy powder
- tzm
- equal
- alloy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
- B22F9/14—Making metallic powder or suspensions thereof using physical processes using electric discharge
-
- 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
Abstract
The invention provides a preparation method of spherical TZM alloy powder, belonging to the technical field of metal powder material preparation. The invention uses reduced molybdenum (Mo) powder and titanium hydride (TiH)2) Powder, zirconium hydride (ZrH)2) The powder and graphite powder are used as basic raw materials to prepare the raw powder which meets the alloy stoichiometry. Adding anhydrous ethanol into the raw powder to prepare slurry, and fully stirring to uniformly mix the slurry. And drying the slurry in vacuum, and sintering the powder in a reducing atmosphere. And (3) performing ball milling on the blank after the alloy powder is sintered to fully crush the blank. And screening the alloy powder subjected to ball milling, and selecting irregular TZM alloy powder within a certain particle size range. And (3) feeding the irregular TZM alloy powder into an induction coupling plasma torch, rapidly melting the TZM alloy powder under the action of high temperature, and forming a spherical molten alloy drop under the action of surface tension. And (3) separating the molten spherical TZM alloy liquid drops from the plasma high-temperature area, and rapidly cooling under the protection of inert gas to form spherical TZM alloy powder.
Description
Technical Field
The invention belongs to the technical field of alloy powder material preparation, and particularly relates to a method for preparing a molybdenum (Mo) powder and titanium hydride (TiH) powder by reduction2) Powder, zirconium hydride (ZrH)2) A method for preparing spherical molybdenum-titanium-zirconium (TZM) alloy powder by using powder and graphite powder as raw materials.
Background
The Molybdenum alloy is a non-ferrous alloy formed by adding other elements by taking Molybdenum as a matrix, and the Molybdenum-Titanium-Zirconium alloy (Titanium-Zirconium-Molybdenum, TZM, 0.4-0.55% of Ti, 0.06-0.12% of Zr, 0.01-0.04% of C and Mo Bal) is the most widely applied Molybdenum-based alloy at present. The high-elasticity molybdenum alloy has the advantages of high elastic modulus, low expansion coefficient, low saturated vapor pressure, creep resistance, corrosion resistance and the like while retaining the high melting point, high strength, wear resistance and excellent thermal and electrical conductivity of molybdenum metal. Therefore, the TZM alloy is widely used for processing high-temperature structural materials and applied to the fields of equipment manufacturing, petrochemical industry, aerospace, military industry, nuclear power industry and the like. Particularly, the TZM alloy has the advantages of high temperature resistance, ablation resistance, strong heat resistance, high-speed airflow scouring resistance and the like, and shows good mechanical properties at high temperature and high pressure, so that the TZM alloy is used for manufacturing rocket nozzles, solid engine gas valve bodies and the like.
However, the TZM alloy belongs to a hard and brittle material, and the Ti and Zr elements are added into the alloy, so that the alloy is strengthened and toughened, thereby bringing great difficulty to the mechanical processing of the TZM alloy. The material has low impact toughness, small elongation, small linear expansion coefficient, high elastic modulus and less elastic deformation. Fracture occurs with little to no significant macroscopic deformation during processing. Therefore, the traditional cutting process is easy to crack, fall scraps, crush, strip-shaped fall off and even break, the surface quality of the processed part is poor, and the tool is seriously worn. Meanwhile, some processing elements of the TZM alloy part, such as special-shaped holes, narrow grooves, complex cavities and the like, have obvious obstacles in the processing process.
The rapid development of aerospace and other high-end technologies has dramatically increased the demand for high-performance and high-precision TZM alloy products with complex shapes and uniform structures. Due to the advantages of rapidness, flexibility, material saving and personalized customization, the additive manufacturing technology has obvious advantages in the aspects of processing and forming of parts with high melting points, high performance and complex geometric shapes of traditional difficult-to-process materials, and is an important development direction of advanced manufacturing technology.
The spherical TZM alloy powder is a material basis for the development of the additive manufacturing technology of the TZM alloy part, and the composition, the appearance and the particle size of the spherical TZM alloy powder directly influence the quality and the performance of the additive manufactured TZM alloy part. The TZM alloy powder used for additive manufacturing needs to have the characteristics of good sphericity, high compactness, low oxygen content and the like, and also needs to have uniform and controllable particle size, and can be industrially produced in batches at lower cost.
At present, no mature preparation technology is available at home and abroad, and is suitable for the production of TZM alloy powder for additive manufacturing. Although the process of the TZM alloy powder developed for the traditional powder metallurgy industry is mature and the cost is low, the prepared TZM alloy powder has irregular appearance and low density, the powder agglomeration phenomenon is serious, the fluidity is poor, and the requirement of the additive manufacturing technology on the high-performance TZM alloy powder is difficult to meet, so that the preparation of the high-performance TZM alloy powder for additive manufacturing, which has uniform particle size distribution, low impurity content, high density and good fluidity, becomes a difficult problem to be solved urgently in technical development.
Disclosure of Invention
The invention aims to design a preparation method of spherical TZM alloy powder aiming at the problems of poor flowability, low density, irregular appearance and the like of the TZM alloy powder prepared by the existing production process. The method aims to prepare the spherical TZM alloy powder with uniform particle size distribution, low impurity content, high density and good fluidity so as to meet the urgent need of the additive manufacturing field for the high-performance TZM alloy powder.
To achieve the above object, the solution of the present invention is as follows:
a method of preparing a spherical TZM alloy powder comprising the steps of:
step 1: preparing and mixing reduced molybdenum powder, titanium hydride powder, zirconium hydride powder and graphite powder according to the alloy stoichiometry to obtain raw material powder according with the alloy component ratio;
step 2: adding absolute ethyl alcohol into the raw material powder conforming to the alloy components to prepare slurry; pouring the slurry into a three-dimensional mixer, fully stirring to completely soak the slurry, and uniformly mixing;
and step 3: and (3) drying the slurry uniformly mixed in the step (2) in a protective atmosphere, and sintering the dried slurry in a reducing atmosphere to obtain a sintered blank.
And 4, step 4: mechanically crushing the alloy powder sintered blank obtained in the step 3, then carrying out ball milling to ensure that the blank is fully deformed and crushed to a particle size of less than 200 mu m, and cooling;
and 5: screening the alloy powder subjected to ball milling, and selecting irregular TZM alloy powder with the required particle size range;
step 6: establishing an inductively coupled plasma torch;
and 7: conveying the irregular TZM alloy powder selected in the step 5 to a plasma torch core area by using carrier gas, heating and melting the TZM alloy powder to form alloy molten drops, and densifying and spheroidizing the alloy molten drops under the action of surface tension;
and 8: and (4) separating the alloy molten drops from the core area of the plasma torch, and cooling and solidifying the alloy molten drops in the inert gas atmosphere to obtain the spherical compact TZM alloy powder.
Specifically, the particle size range of the reduced molybdenum powder in the step 1 is 0.1-5 μm, the purity is more than or equal to 99.9 wt%, and the oxygen content is less than or equal to 0.05 wt%; the granularity range of the titanium hydride powder is 0.1-5 mu m, the purity is more than or equal to 99.80 wt%, and the oxygen content is less than or equal to 0.05 wt%; the particle size range of the zirconium hydride powder is 0.1-5 mu m, the purity is more than or equal to 99.8 wt%, and the oxygen content is less than or equal to 0.05 wt%; the particle size range of the graphite powder is 1-30 mu m, the purity is more than or equal to 99.9 wt% in terms of mass fraction, and the oxygen content is less than or equal to 0.05 wt%.
Specifically, in the step 2, the absolute ethyl alcohol is analytically pure, and the mass percentage of the solid phase in the prepared slurry is 40-70%; the material of a mixing tank of the three-dimensional mixer for mixing the slurry is pure molybdenum, the tank body is sealed in the mixing process, 99.9 wt% of argon is filled into the tank for atmosphere protection, and the mixing time is 2-5 hours.
Specifically, in the step 3, drying the slurry by using a vacuum drying oven under the protection atmosphere of argon with the purity of 99.9 wt%, wherein the drying temperature is 60-90 ℃, and the drying time is 2-5 h; sintering the powder by using a hydrogen atmosphere furnace, wherein the sintering atmosphere is 99.99 wt% of hydrogen, the sintering temperature is 700-900 ℃, and the sintering time is 2-5 h; after sintering, the mixture is cooled to room temperature along with the furnace under the atmosphere of 99.99 wt% hydrogen.
Specifically, in the step 4, the ball milling equipment is a planetary ball mill, the material of the ball milling tank body is pure molybdenum, molybdenum balls with the ball diameters of phi 2mm, phi 5mm and phi 10mm are used as milling bodies, and the adding proportion of the three balls is 6:3: 1. The ball-material ratio is 5:1, and the ball milling speed is 120r/min-180 r/min. And in the ball milling process, the tank body is sealed, 99.9 wt% of argon is filled into the tank for atmosphere protection, and the ball milling time is 3-9 h. After ball milling, cooling to a temperature lower than 40 ℃, and discharging.
Specifically, the sieving operation of the TZM alloy powder obtained by ball milling in the step 5 is carried out in an argon environment, the used equipment is a rotary vibrating sieve, and the purity of argon is more than or equal to 99.9 wt%.
Specifically, in the step 6, the power of the plasma torch is 45kW-90kW, the working gas is argon, the flow rate is 10s lpm-50s lpm, the side gas is argon, the flow rate is 80s lpm-200s lpm, and the operating ambient pressure of the plasma torch is 40kPa-70 kPa. The purity of the argon is more than or equal to 99.99 wt%.
Specifically, in the step 7, the TZM alloy powder with the required particle size range is fed into the core area of the plasma torch by using a carrier gas, wherein the carrier gas is argon, the flow rate is 10-40 s lpm, and the powder feeding rate of the TZM alloy powder is 20-100 g/min. The purity of the argon is more than or equal to 99.99 wt%.
Specifically, the inert gas atmosphere required by cooling and solidifying the molten TZM alloy in the step 8 is an argon atmosphere, the purity is more than or equal to 99.99 wt%, and the gas temperature is not more than 30 ℃; the cooling speed of the powder is more than or equal to 1 x 104K/s。
Specifically, the particle size range of the spherical TZM alloy powder formed in the step 8 is 10-100 μm, the spheroidization rate is more than 90%, and the purity of the TZM alloy powder is more than 99.5 wt%.
The invention has the beneficial effects that:
(1) the powder blank which accords with the stoichiometry of the TZM alloy is obtained by the methods of powder mixing, drying and sintering, mechanical energy is applied to the alloy powder in a ball milling mode to induce the structure and the physical and chemical properties of the alloy powder to change, so that the state of the alloy raw material powder is optimized, and the alloy powder is favorable for rapidly melting in the spheroidizing process.
(2) Aiming at the problem of wide particle size distribution of irregular powder after ball milling, the invention treats the powder by a method of screening firstly and then spheroidizing, can select TZM alloy powder in a specific particle size range, has narrower powder particle size distribution, is beneficial to process control in the powder spheroidizing process, effectively reduces vaporization and burning loss of the TZM alloy powder in the plasma spheroidizing process, is beneficial to particle size control of the finally spheroidized TZM alloy powder, and greatly improves the production efficiency and the product quality.
(3) The high-temperature plasma for powder spheroidization is excited by the induction coil, so that the problem of material pollution caused by burning loss of an electrode does not exist; meanwhile, the operations of mixing, drying, ball milling, screening, spheroidizing, cooling and collecting of TZM alloy powder are carried out under the protective atmosphere of argon, so that the impurity content of the product is effectively controlled.
(4) After the TZM alloy powder is melted in high-temperature plasma, the internal defects of the material can be eliminated under the action of surface tension, and a smooth and compact structure is obtained; after the alloy molten drop is separated from the high-temperature plasma torch, the molten drop is separated by 1 multiplied by 104The rapid solidification is carried out at the speed of K/s, and the obtained spherical powder not only keeps a smooth and compact structure, but also refines the structure.
(5) The method adopts reduced molybdenum (Mo) powder and titanium hydride (TiH)2) Powder, zirconium hydride (ZrH)2) The powder and the graphite powder are basic raw materials, so that the raw materials are high in purity and easy to obtain, and the cost is low; after the powder is uniformly mixed, the particle size range of the spherical TZM alloy powder can be effectively controlled by the methods of drying, sintering, ball milling and screening; in the process of spheroidizing the TZM alloy powder, vaporization and burning loss in the process of spheroidizing the TZM alloy powder can be effectively reduced by controlling the feeding rate and matching spheroidizing process parameters such as input power, gas flow and the like, and the production process is stable; and finally, the operations of sieving, spheroidizing, cooling and collecting the TZM alloy powder are carried out under the protective atmosphere of argon, so that the oxygen content of the product is effectively reduced.
Drawings
FIG. 1 is a process flow diagram of a method of preparing spherical TZM alloy powder according to the present invention;
FIG. 2 is a schematic view of a spheroidization process of TZM alloy powder in an inductively coupled plasma torch according to the present invention;
FIG. 3 is a scanning electron micrograph of 20 μm to 45 μm TZM (0.4Ti-0.08Zr-0.03C-Mo) alloy powder prepared in example 1 of the present invention;
FIG. 4 is a scanning electron micrograph of 53 μm to 90 μm spherical TZM (0.5Ti-0.1Zr-0.02C-Mo) alloy powder prepared in example 2 of the present invention;
FIG. 5 is a scanning electron micrograph of 30 μm to 75 μm spherical TZM (0.45Ti-0.08Zr-0.03C-Mo) alloy powder prepared in example 3 of the present invention.
Detailed Description
Preferred embodiments of the present invention will be described in detail below with reference to the accompanying drawings. It will be understood by those skilled in the art that the present invention is not limited thereto and that any modifications and variations made based on the present invention are within the scope of the present invention.
The following are several specific embodiments of the invention:
example 1
Preparing low oxygen spherical TZM (0.4Ti-0.08Zr-0.03C-Mo) alloy powder with a particle size range of 20 μm to 45 μm, comprising the steps of:
step 1: zirconium hydride (ZrH) with the granularity of 2 mu m to 5 mu m and the purity of more than or equal to 99.9wt percent is doped into reduced molybdenum powder with the granularity of 2 mu m to 3 mu m and the purity of more than or equal to 99.9wt percent2) Powder, 0.4% titanium hydride powder (TiH) with granularity of 2-5 μm and purity of more than or equal to 99.80 wt%2) 0.03 percent of graphite powder with the granularity of 10-25 mu m and the purity of more than or equal to 99.9wt percent is prepared into TZM raw material powder with the stoichiometric number of 0.4Ti-0.08 Zr-0.03C-Mo.
Step 2: adding analytically pure absolute ethyl alcohol into TZM raw material powder to prepare slurry with the solid phase mass percentage content of 60%;
and step 3: pouring the slurry into a molybdenum mixing tank of a three-dimensional mixer, filling 99.9 wt% of argon into the mixing tank for atmosphere protection, then sealing the mixing tank, and mixing the materials for 3 hours until the slurry is completely soaked and uniformly mixed;
and 4, step 4: drying the uniformly mixed slurry by using a vacuum drying oven under the protection atmosphere of argon with the purity of 99.9 wt%, wherein the drying temperature is 73 ℃, and the drying time is 3 hours; sintering the powder by using a hydrogen atmosphere furnace, wherein the sintering atmosphere is 99.99 wt% of hydrogen atmosphere, the sintering temperature is 770 ℃, and the sintering time is 3.5 h; after the sintering is finished, the mixture is cooled to room temperature along with the furnace in a hydrogen atmosphere with the purity of 99.99 wt%.
And 5: and putting the sintered alloy blank into a planetary ball mill of a molybdenum ball mill tank body for ball milling, wherein molybdenum balls with the ball diameters of phi 2mm, phi 5mm and phi 10mm are used as milling bodies, and the putting ratio of the three balls is 6:3: 1. The ball-material ratio is 5:1, and the ball milling speed is 150 r/min. And in the ball milling process, the tank body is sealed, 99.9 wt% of argon is filled into the tank for atmosphere protection, and the ball milling time is 5 hours. And after ball milling, naturally cooling for 2 hours, and discharging when the temperature is lower than 40 ℃.
Step 6: and (3) screening the ball-milled TZM alloy powder by adopting a rotary vibration screen under the argon atmosphere with the purity of more than or equal to 99.9 wt%, and arranging two layers of screens, wherein the aperture of the upper layer screen is 325 meshes, and the aperture of the lower layer screen is 600 meshes. The alloy powder remaining on the 600 mesh screen was collected.
And 7: establishing an inductively coupled plasma torch with the power of 60kW, wherein the basic structure of the plasma torch is shown in figure 2; the working gas of the plasma torch is argon with the purity of more than or equal to 99.99 wt%, the flow rate is 20s lpm, the side gas is argon with the purity of more than or equal to 99.99 wt%, and the flow rate is 120s lpm; the plasma torch was operated at an ambient pressure of 50 kPa.
And 8: argon with the purity of more than or equal to 99.99 wt% is used as a carrier gas, the TZM alloy powder is conveyed to the core area of the plasma torch through a powder conveying pipe, the carrier gas flow is 15s lpm, the powder conveying speed of the TZM alloy powder is 40g/min, and the TZM alloy powder is melted in the plasma torch.
And step 9: the molten TZM alloy powder is cooled and solidified under the atmosphere temperature of 25 ℃ and the argon atmosphere with the purity of more than or equal to 99.99 wt%, and low-oxygen spherical TZM (0.4Ti-0.08Zr-0.03C-Mo) alloy powder with the particle size range of 20-45 mu m is obtained, and the scanning electron microscope picture is shown in figure 3, the spheroidization rate is 91%, and the purity of the alloy powder is 99.7 wt%.
Example 2
Preparing spherical (0.5Ti-0.1Zr-0.02C-Mo) TZM alloy powder with a particle size ranging from 53 μm to 90 μm, comprising the steps of:
step 1: zirconium hydride (ZrH) with the granularity of 2-5 mu m is doped in 0.1 percent (mass fraction, the same below) of reduced molybdenum powder with the granularity of 3-5 mu m2) Powder, 0.5% titanium hydride powder (TiH) with the granularity of 0.5-3 mu m2) 0.02% of graphite powder with the particle size of 12-20 mu m, and preparing TZM raw material powder with the stoichiometric number of 0.5Ti-0.1 Zr-0.02C-Mo.
Step 2: adding analytically pure absolute ethyl alcohol into TZM raw material powder to prepare slurry with the solid phase mass percentage content of 50%;
and step 3: pouring the slurry into a molybdenum mixing tank of a three-dimensional mixer, filling 99.9 wt% of argon into the mixing tank for atmosphere protection, then sealing the mixing tank, and mixing the materials for 3 hours until the slurry is completely soaked and uniformly mixed;
and 4, step 4: drying the uniformly mixed slurry by using a vacuum drying oven under the protection atmosphere of argon with the purity of 99.95 wt%, wherein the drying temperature is 75 ℃, and the drying time is 3.5 h; sintering the powder by using a hydrogen atmosphere furnace, wherein the sintering atmosphere is 99.99 wt% of hydrogen, the sintering temperature is 700-750 ℃, and the sintering time is 3 h; after sintering, the mixture is cooled to room temperature along with the furnace under the atmosphere of 99.99 wt% hydrogen.
And 5: and putting the sintered alloy blank into a planetary ball mill of a molybdenum ball mill tank body for ball milling, wherein molybdenum balls with the ball diameters of phi 2mm, phi 5mm and phi 10mm are used as milling bodies, and the putting ratio of the three balls is 6:3: 1. The ball-material ratio is 5:1, and the ball milling speed is 180 r/min. And in the ball milling process, the tank body is sealed, 99.95 wt% of argon is filled into the tank for atmosphere protection, and the ball milling time is 4 hours. And naturally cooling for 3 hours after ball milling, and discharging when the temperature is lower than 40 ℃.
Step 6: and (3) screening the ball-milled TZM alloy powder by adopting a rotary vibration screen under the argon atmosphere with the purity of more than or equal to 99.95 wt%, and arranging two layers of screens, wherein the aperture of the upper layer screen is 150 meshes, and the aperture of the lower layer screen is 270 meshes. The alloy powder remaining on the 270 mesh screen was collected.
And 7: establishing a basic structure of an inductively coupled plasma torch as shown in figure 2, wherein the power of the plasma torch is 75 kW; the working gas of the plasma torch is argon with the purity of more than or equal to 99.99 wt%, the flow rate is 30s lpm, the side gas is argon with the purity of more than or equal to 99.99 wt%, and the flow rate is 130s lpm; the plasma torch was operated at an ambient pressure of 60 kPa.
And 8: argon with the purity of more than or equal to 99.99 wt% is used as a carrier gas, the TZM alloy powder is conveyed to the core area of the plasma torch through a powder conveying pipe, the carrier gas flow is 20s lpm, the powder conveying speed of the TZM alloy powder is 45g/min, and the TZM alloy powder is melted in the plasma torch.
And step 9: the molten TZM alloy powder is cooled and solidified under the atmosphere temperature of 27 ℃ and the argon atmosphere with the purity of more than or equal to 99.99 wt%, and the obtained spherical TZM (0.5Ti-0.1Zr-0.02C-Mo) alloy powder with the particle size range of 53-90 μm is shown in figure 4 by a scanning electron microscope photograph, wherein the spheroidization rate is 93% and the purity is 99.8 wt%.
Example 3
Preparing spherical (0.45Ti-0.08Zr-0.03C-Mo) TZM alloy powder with a particle size ranging from 30 μm to 75 μm, comprising the steps of:
step 1: the reduced molybdenum powder with the granularity of 3-5 mu m is doped with 00.8% (mass fraction, the same below) of zirconium hydride (ZrH) with the granularity of 2-5 mu m2) Powder and 0.45% of titanium hydride powder (TiH) with the granularity of 0.5-3 mu m2) 0.03 percent of graphite powder with the granularity of 12-20 mu m, and TZM raw material powder with the stoichiometric number of 0.45Ti-0.08Zr-0.03C-Mo is prepared.
Step 2: adding analytically pure absolute ethyl alcohol into TZM raw material powder to prepare slurry with the solid phase mass percentage of 55%;
and step 3: pouring the slurry into a molybdenum mixing tank of a three-dimensional mixer, filling 99.9 wt% of argon into the mixing tank for atmosphere protection, sealing the mixing tank, and mixing for 3.5 hours until the slurry is completely soaked and uniformly mixed;
and 4, step 4: drying the uniformly mixed slurry by using a vacuum drying oven under the protection atmosphere of argon with the purity of 99.9 wt%, wherein the drying temperature is 75 ℃, and the drying time is 2 hours; sintering the powder by using a hydrogen atmosphere furnace, wherein the sintering atmosphere is 99.99 wt% of hydrogen, the sintering temperature is 780 ℃, and the sintering time is 4 hours; after sintering, the mixture is cooled to room temperature along with the furnace under the atmosphere of 99.99 wt% hydrogen.
And 5: and putting the sintered alloy blank into a planetary ball mill of a molybdenum ball mill tank body for ball milling, wherein molybdenum balls with the ball diameters of phi 2mm, phi 5mm and phi 10mm are used as milling bodies, and the putting ratio of the three balls is 6:3: 1. The ball-material ratio is 5:1, and the ball milling speed is 160 r/min. And in the ball milling process, the tank body is sealed, 99.95 wt% of argon is filled into the tank for atmosphere protection, and the ball milling time is 4.5 hours. And (5) naturally cooling after ball milling, and discharging when the temperature is lower than 40 ℃.
Step 6: and (3) screening the ball-milled TZM alloy powder by adopting a rotary vibration screen under the argon atmosphere with the purity of more than or equal to 99.95 wt%, and arranging two layers of screens, wherein the aperture of the upper layer screen is 200 meshes, and the aperture of the lower layer screen is 500 meshes. The alloy powder remaining on the 500 mesh screen was collected.
And 7: establishing a basic structure of an inductively coupled plasma torch as shown in figure 2, wherein the power of the plasma torch is 70 kW; the working gas of the plasma torch is argon with the purity of more than or equal to 99.99 wt%, the flow rate is 25s lpm, the side gas is argon with the purity of more than or equal to 99.99 wt%, and the flow rate is 125s lpm; the plasma torch was operated at an ambient pressure of 65 kPa.
And 8: argon with the purity of more than or equal to 99.99 wt% is used as a carrier gas, the TZM alloy powder is conveyed to the core area of the plasma torch through a powder conveying pipe, the carrier gas flow is 25s lpm, the powder conveying speed of the TZM alloy powder is 40g/min, and the TZM alloy powder is melted in the plasma torch.
And step 9: the molten TZM alloy powder is cooled and solidified under the atmosphere temperature of 25 ℃ and the argon atmosphere with the purity of more than or equal to 99.99 wt%, and the obtained spherical TZM (0.45Ti-0.08Zr-0.03C-Mo) alloy powder with the grain diameter range of 30-75 μm is shown in figure 5 by a scanning electron microscope photograph, wherein the spheroidization rate is 92% and the purity is 99.6 wt%.
The foregoing specific embodiments are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims. The present invention is not disclosed in the technical field of the common general knowledge of the technicians in this field.
Claims (11)
1. The preparation method of the spherical TZM alloy powder is characterized by comprising the following steps:
step 1: preparing and mixing reduced molybdenum powder, titanium hydride powder, zirconium hydride powder and graphite powder according to the alloy stoichiometry to obtain raw material powder according with the alloy component ratio; the granularity range of the reduced molybdenum powder in the step 1 is 0.1-5 mu m, the purity is more than or equal to 99.9 wt%, and the oxygen content is less than or equal to 0.05 wt%; the granularity range of the titanium hydride powder is 0.1-5 mu m, the purity is more than or equal to 99.80 wt%, and the oxygen content is less than or equal to 0.05 wt%; the particle size range of the zirconium hydride powder is 0.1-5 mu m, the purity is more than or equal to 99.8 wt%, and the oxygen content is less than or equal to 0.05 wt%; the granularity range of the graphite powder is 1-30 mu m, the purity is more than or equal to 99.9 wt% in terms of mass fraction, and the oxygen content is less than or equal to 0.05 wt%;
step 2: adding absolute ethyl alcohol into the raw material powder which is obtained in the step 1 and accords with the alloy components to prepare slurry, and stirring and mixing the slurry uniformly;
and step 3: drying the slurry uniformly mixed in the step 2 in a protective atmosphere, and sintering the dried slurry in a reducing atmosphere to obtain a sintered blank;
and 4, step 4: crushing the alloy powder sintered blank obtained in the step 3, then carrying out ball milling to ensure that the blank is fully crushed until the grain size is less than 200 mu m, and cooling;
and 5: screening the alloy powder subjected to ball milling, and selecting irregular TZM alloy powder with the required particle size range;
step 6: establishing an inductively coupled plasma torch;
and 7: conveying the irregular TZM alloy powder selected in the step 5 to a plasma torch core area by using carrier gas, heating and melting the TZM alloy powder to form alloy molten drops, and densifying and spheroidizing the alloy molten drops under the action of surface tension;
and 8: separating the molten alloy drop from the core region of the plasma torch, cooling and solidifying at a temperature of no more than 30 ℃ in an inert gas atmosphere, wherein the powder cooling speed is not less than 1 x 104K/s to obtain the spherical compact TZM alloy powder.
2. The method of claim 1, further comprising: in the step 2, the absolute ethyl alcohol is analytically pure, and the mass percentage of the solid phase in the prepared slurry is 40-70%.
3. The method of claim 1, further comprising: and 2, uniformly stirring and mixing the slurry in the step 2 through a mixer, wherein a mixing tank arranged on the mixer is made of pure molybdenum, the tank body is sealed in the mixing process, argon is filled into the tank for atmosphere protection, and the mixing time is 2-5 hours.
4. The method of claim 1, further comprising: in the step 3, drying the slurry by using a vacuum drying oven under the protection of argon at the drying temperature of 60-90 ℃ for 2-5 h; sintering the dried alloy powder by using a hydrogen atmosphere reduction furnace, wherein the sintering atmosphere is hydrogen, the sintering temperature is 700-900 ℃, and the sintering time is 2-5 h; after sintering, cooling to room temperature along with the furnace under the hydrogen protective atmosphere; the purity of the hydrogen is more than or equal to 99.99 wt% in the sintering and cooling processes.
5. The method of claim 1, further comprising: and 4, the material of the pot body of the ball mill used in the ball mill in the step 4 is pure molybdenum, the molybdenum balls are used as grinding bodies, and the ball mill is cooled to the temperature lower than 40 ℃ after the ball milling is finished.
6. The method of claim 5, further comprising: the ball mill is a planetary ball mill, and the ball diameters of molybdenum balls thrown into a ball milling tank body are phi 2mm, phi 5mm and phi 10mm respectively; the adding proportion of the three molybdenum balls is 6:3: 1; the ball-material ratio is 5:1, and the ball milling rotating speed is 120r/min-180 r/min; and in the ball milling process, the tank body is sealed and filled with argon for protection, and the ball milling time is 3-9 h.
7. The method of claim 1, further comprising: and 5, screening the TZM alloy powder obtained by ball milling in the argon atmosphere.
8. The method of claim 1, further comprising: in the step 6, the power of the plasma torch is 45kW to 90kW, the working gas is argon, and the flow is 10slpm to 50 slpm; the side gas is argon, and the flow rate is 80 slpm-200 slpm; the operating ambient pressure of the plasma torch is 40-70 kPa; the purity of the argon is more than or equal to 99.99 wt%.
9. The method of claim 1, further comprising: in the step 7, the carrier gas is argon, the purity is more than or equal to 99.99 wt%, and the flow is 10 slpm-40 slpm; the powder feeding speed of the TZM alloy powder is 20g/min-100 g/min.
10. The method of claim 3 or 4 or 6 or 7, wherein: the purity of the argon is more than or equal to 99.9 wt%.
11. The method of claim 1, further comprising: the grain diameter range of the spherical TZM alloy powder formed in the step 8 is 10-100 mu m, the spheroidization rate is more than 90 percent, and the purity of the TZM alloy powder is more than 99.5 percent by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811101638.9A CN109332717B (en) | 2018-09-20 | 2018-09-20 | Preparation method of spherical molybdenum titanium zirconium alloy powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811101638.9A CN109332717B (en) | 2018-09-20 | 2018-09-20 | Preparation method of spherical molybdenum titanium zirconium alloy powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109332717A CN109332717A (en) | 2019-02-15 |
| CN109332717B true CN109332717B (en) | 2022-01-25 |
Family
ID=65305941
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811101638.9A Active CN109332717B (en) | 2018-09-20 | 2018-09-20 | Preparation method of spherical molybdenum titanium zirconium alloy powder |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109332717B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111097919B (en) * | 2019-12-16 | 2021-11-26 | 中南大学 | Preparation method of multi-component refractory alloy spherical powder |
| CN111515408B (en) * | 2020-05-12 | 2022-12-06 | 广东省材料与加工研究所 | NiTi alloy powder and preparation method and application thereof |
| CN115612904B (en) * | 2022-08-26 | 2023-06-30 | 洛阳科威钨钼有限公司 | High-hardness TZM alloy and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1962911A (en) * | 2006-12-15 | 2007-05-16 | 西部金属材料股份有限公司 | Process for preparing molybdenum alloy TZM by powder metallurgy |
| CN101250635A (en) * | 2008-04-11 | 2008-08-27 | 中南大学 | Method for manufacturing high performance sinter Mo-Ti-Zr molybdenum alloy |
| CN101934372A (en) * | 2010-07-30 | 2011-01-05 | 西北有色金属研究院 | Method for preparing large powder metallurgy TZM blank with uniform carbon and oxygen distribution |
| CN102534333A (en) * | 2012-01-05 | 2012-07-04 | 西安建筑科技大学 | Method for preparing fine-grain high-density TZM (Titanium-Zirconium-Molybdenum Allo) alloy |
| CN105562700A (en) * | 2015-12-31 | 2016-05-11 | 龙岩紫荆创新研究院 | Plasma preparation method of spherical titanium powder for 3D printing |
| CN107309434A (en) * | 2017-06-06 | 2017-11-03 | 中国航天空气动力技术研究院 | A kind of preparation method and application of the spherical molybdenum powder of high-purity compact |
| CN107363262A (en) * | 2017-06-06 | 2017-11-21 | 中国航天空气动力技术研究院 | A kind of preparation method and application of high-purity compact spherical titanium zirconium alloy powder |
-
2018
- 2018-09-20 CN CN201811101638.9A patent/CN109332717B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1962911A (en) * | 2006-12-15 | 2007-05-16 | 西部金属材料股份有限公司 | Process for preparing molybdenum alloy TZM by powder metallurgy |
| CN101250635A (en) * | 2008-04-11 | 2008-08-27 | 中南大学 | Method for manufacturing high performance sinter Mo-Ti-Zr molybdenum alloy |
| CN101934372A (en) * | 2010-07-30 | 2011-01-05 | 西北有色金属研究院 | Method for preparing large powder metallurgy TZM blank with uniform carbon and oxygen distribution |
| CN102534333A (en) * | 2012-01-05 | 2012-07-04 | 西安建筑科技大学 | Method for preparing fine-grain high-density TZM (Titanium-Zirconium-Molybdenum Allo) alloy |
| CN105562700A (en) * | 2015-12-31 | 2016-05-11 | 龙岩紫荆创新研究院 | Plasma preparation method of spherical titanium powder for 3D printing |
| CN107309434A (en) * | 2017-06-06 | 2017-11-03 | 中国航天空气动力技术研究院 | A kind of preparation method and application of the spherical molybdenum powder of high-purity compact |
| CN107363262A (en) * | 2017-06-06 | 2017-11-21 | 中国航天空气动力技术研究院 | A kind of preparation method and application of high-purity compact spherical titanium zirconium alloy powder |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109332717A (en) | 2019-02-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107363262B (en) | Preparation method and application of high-purity compact spherical titanium-zirconium alloy powder | |
| CN107309434B (en) | Preparation method and application of high-purity compact spherical molybdenum powder | |
| CN111940723A (en) | Nano ceramic metal composite powder for 3D printing and application | |
| CN109434117B (en) | Preparation method of spherical zirconium-niobium alloy powder for 3D printing | |
| CN105506345B (en) | High heat-conductive diamond/copper composite encapsulating material and preparation method thereof | |
| CN109332717B (en) | Preparation method of spherical molybdenum titanium zirconium alloy powder | |
| CN111097919B (en) | Preparation method of multi-component refractory alloy spherical powder | |
| CN109332695B (en) | Selective laser melting preparation method of molybdenum-based alloy with enhanced oxidation resistance | |
| CN100465309C (en) | Method for preparing alloy material of high niobium-titanium-aluminum by discharging plasma agglomeration | |
| CN102534333A (en) | Method for preparing fine-grain high-density TZM (Titanium-Zirconium-Molybdenum Allo) alloy | |
| CN107971499A (en) | The method for preparing spherical titanium aluminium-based alloyed powder end | |
| CN106756168B (en) | The method that one kind prepares Ti (C, N) based ceramic metal based on carbon thermal reduction molybdenum trioxide | |
| CN115044794A (en) | Cu- (Y) with excellent performance 2 O 3 -HfO 2 ) Alloy and preparation method thereof | |
| CN113337786B (en) | Nano zirconium oxide/amorphous alloy composite material and preparation method thereof | |
| CN107952966A (en) | The preparation method at spherical titanium aluminium-based alloyed powder end | |
| CN107502771A (en) | A kind of preparation method of nano-TiC particle reinforced aluminum matrix composites | |
| CN114703394A (en) | High-temperature material and preparation method and application thereof | |
| CN107841669B (en) | High-thermal-conductivity active composite packaging material and preparation method thereof | |
| CN113889563A (en) | P-type bismuth telluride-based thermoelectric material and preparation method and application thereof | |
| CN116287833A (en) | Preparation method of in-situ authigenic two-dimensional carbide dispersion strengthening and toughening molybdenum alloy | |
| CN108044122B (en) | Preparation method of Nb-Si-based alloy hollow turbine blade | |
| CN114182127B (en) | High-performance in-situ reinforced titanium-based composite material and preparation process thereof | |
| CN113862507B (en) | Preparation method of high-density high-copper-content copper-tungsten composite material | |
| CN113843415B (en) | Tantalum-niobium alloy powder and preparation method thereof | |
| CN113275594B (en) | Selective laser melting forming preparation method of high-density molybdenum alloy |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20210426 Address after: 618 Liangjiang Avenue, Yubei District, Chongqing Applicant after: Yunhang times (Chongqing) Technology Co.,Ltd. Address before: 100074, No. 17 Yungang West Road, Beijing, Fengtai District Applicant before: CHINA ACADEMY OF AEROSPACE AERODYNAMICS |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |