CN113430439A - Phase distribution uniformity control method of high-toughness active tungsten alloy - Google Patents

Phase distribution uniformity control method of high-toughness active tungsten alloy Download PDF

Info

Publication number
CN113430439A
CN113430439A CN202110717474.8A CN202110717474A CN113430439A CN 113430439 A CN113430439 A CN 113430439A CN 202110717474 A CN202110717474 A CN 202110717474A CN 113430439 A CN113430439 A CN 113430439A
Authority
CN
China
Prior art keywords
powder
mixing
active
toughness
tungsten 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.)
Granted
Application number
CN202110717474.8A
Other languages
Chinese (zh)
Other versions
CN113430439B (en
Inventor
刘金旭
刘天宇
刘兴伟
幸丽娜
王凯华
司胜平
贺川
蔡奇
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Beijing Institute of Technology BIT
Original Assignee
Beijing Institute of Technology BIT
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Beijing Institute of Technology BIT filed Critical Beijing Institute of Technology BIT
Priority to CN202110717474.8A priority Critical patent/CN113430439B/en
Publication of CN113430439A publication Critical patent/CN113430439A/en
Application granted granted Critical
Publication of CN113430439B publication Critical patent/CN113430439B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/02—Compacting only
    • B22F3/04—Compacting only by applying fluid pressure, e.g. by cold isostatic pressing [CIP]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/12—Both compacting and sintering
    • B22F3/14—Both compacting and sintering simultaneously
    • B22F3/15—Hot isostatic pressing
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/045—Alloys based on refractory metals

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Fluid Mechanics (AREA)
  • Powder Metallurgy (AREA)

Abstract

The invention provides a method for controlling the phase distribution uniformity of a high-toughness active tungsten alloy, and relates to the technical field of powder metallurgy. The invention takes W, Ta/Nb/Ti (one or more of the materials), Zr/Hf/ZrH2/HfH2The (one or more) powder is used as a raw material to prepare the high-toughness active W alloy, and the W and the Ta/Nb/Ti (one or more) are fully and uniformly mixed by a wet mixing method to avoid large-area agglomeration of a certain phase in the sintering process. Meanwhile, W and Ta/Nb/Ti can form a solid solution, Ta/Nb/Ti and Zr can form a solid solution, and W can be reduced under the action of the competitive mechanism2High temperature stability of Zr, and W2Zr is difficult to satisfy the kinetic condition at low temperature, thereby leading the brittle phase W2The nucleation and growth of Zr are inhibited, and the finally obtained active tungsten alloy has ultrahigh strength and good plasticity, so that the active tungsten alloy has wide application prospect.

Description

Phase distribution uniformity control method of high-toughness active tungsten alloy
Technical Field
The invention relates to the technical field of powder metallurgy, in particular to a method for controlling the phase distribution uniformity of a high-toughness active tungsten alloy.
Background
The active W alloy generally refers to W alloy which releases energy under certain external conditions and is obtained by mixing active elements such as W, Zr/Hf and the like according to different components. However, the W alloy is subjected to premature fracture failure during dynamic loading due to the single-phase agglomeration problem in the mixed powder sintering process, and a brittle phase W is inevitably formed in the active W alloy due to the addition of the active element Zr2Zr causes further reduction of the plasticity of the alloy, and severely limits the practical application of the active W alloy.
Disclosure of Invention
The invention aims to provide a method for controlling the phase distribution uniformity of a high-toughness active tungsten alloy, which can enable the active tungsten alloy to have high strength, high density, uniform structure and good plasticity.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a method for controlling the phase distribution uniformity of a high-toughness active tungsten alloy, which comprises the following steps:
wet mixing W powder and solid solution metal powder, and removing the solvent in the obtained liquid material to obtain inactive mixed powder; the solid solution metal powder comprises one or more of Ta powder, Nb powder and Ti powder;
mixing the inactive mixed powder with the activeDry mixing the sexual powder to obtain mixed powder; the active powder comprises Zr powder, Hf powder and ZrH2Powder HfH2One or more of the powders;
carrying out cold isostatic pressing on the mixed powder to obtain a green body;
sintering the green body to obtain a sintered body;
and carrying out hot isostatic pressing on the sintered blank to obtain the high-strength and high-toughness active tungsten alloy.
Preferably, the average particle size of the W powder is 3-25 μm; the average grain diameter of the solid-solution metal powder is 5-45 mu m; the average particle size of the active powder is 5-40 μm.
Preferably, the mass ratio of the W powder to the solid-solution metal powder is 20-80: 5-50.
Preferably, the mass ratio of the inactive mixed powder to the active powder is 40-95: 5-60.
Preferably, the pressure of the cold isostatic pressing is 150-400 MPa, and the pressure maintaining time is 10-60 min.
Preferably, the sintering is fractional pressureless sintering; the sintering procedure comprises: heating the mixture from room temperature to 500 ℃, and keeping the temperature for 0.5-2 h; raising the temperature from 500 ℃ to 800 ℃ and preserving the heat for 1-5 h; raising the temperature from 800 ℃ to 1300-1700 ℃, and preserving the heat for 2-5 h.
Preferably, the sintering is performed under vacuum or protective atmosphere conditions.
Preferably, the pressure of the hot isostatic pressing is 100-200 MPa, the temperature of the hot isostatic pressing is 800-1400 ℃, and the heat preservation and pressure maintaining time is 0.5-2 h.
Preferably, the solvent adopted by the wet mixing is alcohol; the wet mixing mode comprises ball milling mixing, V-shaped mixing, double cone mixing, three-dimensional mixing or double motion mixing.
Preferably, the method for removing the solvent from the liquid material comprises: carrying out suction filtration on the liquid material to obtain a solid substance; the resulting solid material was dried.
The invention provides a method for controlling the phase distribution uniformity of high-toughness active tungsten alloy, which uses W, Ta/Nb/Ti (one or more of the above materials), Zr/Hf/ZrH2/HfH2The (one or more) powder is used as a raw material to prepare the high-toughness active W alloy, and the W and the Ta/Nb/Ti (one or more) are fully and uniformly mixed by a wet mixing method, so that the large-area agglomeration of a certain phase in the sintering process is avoided, and the uniform distribution of the phase is ensured. Meanwhile, W and Ta/Nb/Ti can form a solid solution, Ta/Nb/Ti and Zr can form a solid solution, and W can be reduced under the action of the competitive mechanism2High temperature stability of Zr, and W2Zr is difficult to satisfy the kinetic condition at low temperature, thereby leading the brittle phase W2The nucleation and growth of Zr are inhibited, and the finally obtained active tungsten alloy has ultrahigh strength and good plasticity, so that the active tungsten alloy has wide application prospect. The embodiment result shows that the compressive strength of the active tungsten alloy prepared by the invention is 1800-2200 MPa under the quasi-static loading condition, and the critical failure strain is 10-15%.
In addition, the invention adopts a powder metallurgy process, and the prepared high-strength and high-toughness active tungsten alloy has uniform and compact structure, less pores and no large-area single-phase agglomeration phenomenon. The process has the advantages of short preparation procedure, high efficiency, realization of near-net shape by adopting a method of combining a die with isostatic pressing, less processing excess materials, low cost, realization of batch production and contribution to industrial production.
Drawings
FIG. 1 is a microstructure photograph of a high toughness reactive tungsten alloy prepared in example 1;
FIG. 2 is a graph of compressive stress-strain curves of the high-toughness active tungsten alloys prepared in examples 1-5.
Detailed Description
The invention provides a method for controlling the phase distribution uniformity of a high-toughness active tungsten alloy, which comprises the following steps:
wet mixing W powder and solid solution metal powder, and removing the solvent in the obtained liquid material to obtain inactive mixed powder; the solid solution metal powder comprises one or more of Ta powder, Nb powder and Ti powder;
dry-mixing the inactive mixed powder and the active powder to obtain mixed powder; the active powder comprises Zr powder, Hf powder and ZrH2Powder HfH2One or more of the powders;
carrying out cold isostatic pressing on the mixed powder to obtain a green body;
sintering the green body to obtain a sintered body;
and carrying out hot isostatic pressing on the sintered blank to obtain the high-strength and high-toughness active tungsten alloy.
The invention carries out wet mixing on W powder and solid solution metal powder, removes the solvent in the obtained liquid material and obtains inactive mixed powder. In the invention, the solid solution metal powder comprises one or more of Ta powder, Nb powder and Ti powder; when the solid solution metal powder comprises a plurality of solid solution metal powders, the proportion of the solid solution metal powder does not have special requirements, and the solid solution metal powder can be prepared in any proportion.
In the invention, the average particle size of the W powder is preferably 3-25 μm, and more preferably 3-10 μm; the average particle diameter of the solid-solution metal powder is 5 to 45 [ mu ] m, and more preferably 8 [ mu ] m. The smaller the grain size of the W powder and the solid solution metal powder adopted by the invention is, the more favorable the diffusion of elements in the sintering process is, and the uniformity degree of phase distribution is improved.
In the present invention, the mass ratio of the W powder to the solid-solution metal powder is preferably 20 to 80:5 to 50, and more preferably 75: 25. The invention can improve the strong plasticity matching of the active W alloy within the mass ratio range.
In the present invention, the solvent used for the wet mixing is preferably alcohol; the adding amount of the alcohol is preferably 2-3 cm higher than the powder. In a specific embodiment of the present invention, the W powder and the solid-solution metal powder are added to a mixing vessel, followed by the addition of alcohol.
In the present invention, the wet mixing means preferably includes ball mill mixing, V-type mixing, double cone mixing, three-dimensional mixing or double motion mixing. In the invention, when ball milling mixing is adopted, the rotation speed of the ball milling mixing is preferably 100-300 r/min, and more preferably 200-250 r/min; the time is preferably 5-20 h, and more preferably 8-16 h; the ball-material ratio is preferably 1-4: 1, more preferably 2-3: 1; when V-shaped mixing, double-cone mixing, three-dimensional mixing or double-motion mixing is adopted, the rotating speed is preferably 20-50 r/min, and more preferably 30-40 r/min; the time is preferably 12 to 48 hours, more preferably 15 to 40 hours, and further preferably 20 to 35 hours.
According to the invention, different metal powders are fully and uniformly mixed by controlling the mixing conditions, and the uniformly mixed powder can realize uniform distribution of different elements in the sintering process.
According to the invention, after the wet mixing, the solvent in the obtained liquid material is removed to obtain the inactive mixed powder. In the present invention, the method for removing the solvent preferably includes: carrying out suction filtration on the liquid material obtained by wet mixing to obtain a solid substance; the resulting solid material was dried. In the present invention, the drying is preferably carried out in a vacuum drying oven; the drying temperature is preferably 23-60 ℃, and more preferably 40-60 ℃; the drying time is preferably 5-60 hours, and more preferably 24 hours.
After the inactive mixed powder is obtained, the inactive mixed powder and the active powder are dry-mixed to obtain mixed powder. In the present invention, the active powder includes Zr powder, Hf powder, ZrH powder2Powder HfH2One or more of the powders. In the present invention, the average particle diameter of the active powder is preferably 5 to 40 μm, and more preferably 10 to 20 μm.
In the invention, the mass ratio of the inactive mixed powder to the active powder is preferably 40-95: 5-60, and more preferably 50-90: 10-50.
In the present invention, the dry blending means preferably includes ball mill mixing, V-type mixing, double cone mixing, three-dimensional mixing or double motion mixing. In the invention, when ball milling mixing is adopted, the rotation speed of the ball milling mixing is preferably 100-300 r/min, and more preferably 200-250 r/min; the time is preferably 5-20 h, and more preferably 6-16 h; the ball-material ratio is preferably 1-4: 1, more preferably 2-3: 1; when V-shaped mixing, double-cone mixing, three-dimensional mixing or double-motion mixing is adopted, the rotating speed is preferably 20-50 r/min, and more preferably 30-40 r/min; the time is preferably 12 to 48 hours, more preferably 15 to 40 hours, and further preferably 20 to 35 hours.
According to the invention, dry mixing is adopted when the active powder is added for mixing, so that the oxidation reaction of the active powder can be avoided.
After the mixed powder is obtained, the mixed powder is subjected to cold isostatic pressing to obtain a green body. According to the invention, the rubber mold filled with the mixed powder is preferably placed in the cold isostatic pressing working cavity and pressed under the set process parameters.
In the invention, the pressure of the cold isostatic pressing is preferably 150-400 MPa, more preferably 200-350 MPa, and further preferably 250-320 MPa; the pressure maintaining time is preferably 10 to 60min, more preferably 20 to 50min, and still more preferably 30 to 40 min. The invention adopts cold isostatic pressing to enable the green body to have higher density and density, which is beneficial to subsequent sintering densification.
After a green body is obtained, the green body is sintered to obtain a sintered body. In the present invention, the sintering preferably includes hot press sintering or pressureless sintering, more preferably fractional pressureless sintering. In the present invention, the procedure of the fractional pressureless sintering preferably comprises: heating the mixture from room temperature to 500 ℃, and keeping the temperature for 0.5-2 h; raising the temperature from 500 ℃ to 800 ℃ and preserving the heat for 1-5 h; raising the temperature from 800 ℃ to 1300-1700 ℃, and preserving the heat for 2-5 h. Preferably, the sintering procedure comprises: heating from room temperature to 500 deg.C, and maintaining for 0.5 h; heating from 500 ℃ to 800 ℃ and preserving heat for 1 h; raising the temperature from 800 ℃ to 1500 ℃ and preserving the heat for 3 h.
In the invention, the low-temperature sintering section (500 ℃) can volatilize adsorbed gas and moisture of the green body, meanwhile, the temperature is slowly increased, the low-temperature (500 ℃) and middle-temperature stage (800 ℃) heat preservation time is set to be beneficial to sintering densification of the green body, the high-temperature heat preservation stage (1300-1700 ℃) is a main sintering process, diffusion and flowing among elements are fully carried out to form closed pores and continue to shrink, and alloying and densification are completed.
In the invention, the heating rate of heating from room temperature to 500 ℃ is preferably 1-10 ℃/min, and more preferably 5-7 ℃/min; the heating rate of heating from 500 ℃ to 800 ℃ is preferably 1-10 ℃/min, and more preferably 1-3 ℃/min; the heating rate from 800 ℃ to 1300-1700 ℃ is preferably 1-5 ℃/min, more preferably 2-3 ℃/min.
According to the invention, the heating rate is controlled within the range, so that the green body can be fully dehydrogenated at 500-800 ℃, and the phenomenon of material cracking caused by nonuniform shrinkage in the sintering heating process is reduced.
In the present invention, the sintering is preferably carried out under vacuum or protective atmosphere conditions; the protective atmosphere is preferably an argon atmosphere, the pressure of the argon preferably being 0.1 MPa.
After the sintering, the sintering blank is preferably cooled to room temperature along with the furnace to obtain the sintered blank.
After the sintered blank is obtained, the invention carries out hot isostatic pressing on the sintered blank to obtain the high-strength and high-toughness active tungsten alloy. In the invention, the pressure of the hot isostatic pressing is preferably 100-200 MPa, and more preferably 150-200 MPa; the temperature of the hot isostatic pressing is preferably 800-1400 ℃, and more preferably 1100-1400 ℃; the heat preservation and pressure maintaining time is preferably 0.5-2 h, and more preferably 1 h.
In the present invention, the hot isostatic pressing is preferably carried out under protective atmosphere conditions; the protective atmosphere is preferably an argon atmosphere.
The invention can realize the uniformity regulation and control of the phase distribution of the prepared active W alloy by changing the grain diameter and the proportion of the raw material powder and combining a wet mixing and dry mixing two-step powder mixing process, thereby improving the strong plasticity matching of the active W alloy and meeting the requirements of different application environments by flexibly regulating and controlling the content, the density and the mechanical property of elements in the W alloy.
The method has the advantages of short process flow, low cost and high material utilization rate by adopting a powder metallurgy method, can realize near-net forming of workpieces, can effectively avoid component segregation caused by ingot metallurgy, avoids the problems of thick tissues, shrinkage porosity, shrinkage cavity and the like by adopting the powder metallurgy method, and can meet the requirement of industrial production.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A high-toughness active tungsten alloy comprises the following components in percentage by mass: the preparation process comprises the following steps of:
putting W powder with the average particle size of 3 mu m and Nb powder with the average particle size of 8 mu m into a ball milling tank, wherein the mass of the W powder is 60g, and the mass of the Nb powder is 20 g; mixing powder by adopting a high-energy ball milling method, injecting alcohol into a ball milling tank, wherein the alcohol liquid level is 2cm higher than that of the powder, then installing the ball milling tank on a planetary ball mill for ball milling, wherein the ball-material ratio is 1:1, the ball milling rotation speed is 200r/min, and the ball milling time is 16h to obtain a liquid material; and (3) putting the liquid material into a suction filter funnel for suction filtration, and then putting the solid substance obtained by suction filtration into a vacuum drying oven for drying at the drying temperature of 60 ℃ for 24 hours to obtain the inactive mixed powder.
Mixing the inactive mixed powder with ZrH having an average particle size of 10 μm2Putting the powder into a ball milling tank, wherein the mass of the inactive mixed powder is 80g, and the ZrH2The mass of the powder is 20.44 g; and (3) mounting the ball milling tank on a planetary ball mill for ball milling, wherein the ball-material ratio is 3:1, the ball milling rotation speed is 200r/min, and the ball milling time is 6h, so as to obtain the mixed powder.
And placing the mixed powder into a rubber mold, and performing cold isostatic pressing molding under the pressure of 350MPa for 40min to obtain a green body.
And (2) placing the green body in a sintering furnace for step-by-step pressureless sintering, wherein the process comprises the following steps: heating from room temperature to 500 ℃ at a heating rate of 10 ℃/min, and keeping the temperature at 500 ℃ for 0.5 h; heating from 500 ℃ to 800 ℃ at a heating rate of 1 ℃/min, and keeping the temperature at 800 ℃ for 1 h; heating from 800 ℃ to 1500 ℃ at the heating rate of 2 ℃/min and preserving heat for 3 h; finally, cooling to room temperature along with the furnace to obtain a sintered blank; ar gas of 0.1MPa is introduced as protective gas in the whole sintering process.
And (3) putting the sintered blank into a hot isostatic pressing furnace, introducing Ar gas, keeping the temperature at 1000 ℃, the pressure at 200MPa and the heat and pressure for 1h to obtain the high-strength and high-toughness active tungsten alloy.
Example 2
A high-toughness active tungsten alloy comprises the following components in percentage by mass: the preparation process comprises the following steps of (1) 60% of W, 20% of Ti and 20% of Zr:
putting W powder with the average particle size of 3 mu m and Ti powder with the average particle size of 8 mu m into a ball milling tank, wherein the mass of the W powder is 60g, and the mass of the Ti powder is 20 g; mixing powder by adopting a high-energy ball milling method, injecting alcohol into a ball milling tank, wherein the alcohol liquid level is 2cm higher than that of the powder, then installing the ball milling tank on a planetary ball mill for ball milling, wherein the ball-material ratio is 1:1, the ball milling rotation speed is 200r/min, and the ball milling time is 16h to obtain a liquid material; and (3) putting the liquid material into a suction filter funnel for suction filtration, and then putting the solid substance obtained by suction filtration into a vacuum drying oven for drying at the drying temperature of 60 ℃ for 24 hours to obtain the inactive mixed powder.
Mixing the inactive mixed powder with ZrH having an average particle size of 10 μm2Putting the powder into a ball milling tank, wherein the mass of the inactive mixed powder is 80g, and the ZrH2The mass of the powder is 20.44 g; and (3) mounting the ball milling tank on a planetary ball mill for ball milling, wherein the ball-material ratio is 3:1, the ball milling rotation speed is 200r/min, and the ball milling time is 6h, so as to obtain the mixed powder.
And placing the mixed powder into a rubber mold, and performing cold isostatic pressing molding under the pressure of 350MPa for 40min to obtain a green body.
And (2) placing the green body in a sintering furnace for step-by-step pressureless sintering, wherein the process comprises the following steps: heating from room temperature to 500 ℃ at the heating rate of 7 ℃/min, and keeping the temperature at 500 ℃ for 0.5 h; heating from 500 ℃ to 800 ℃ at a heating rate of 1 ℃/min, and keeping the temperature at 800 ℃ for 1 h; heating from 800 ℃ to 1500 ℃ at the heating rate of 3 ℃/min and preserving heat for 3 h; finally, cooling to room temperature along with the furnace to obtain a sintered blank; ar gas of 0.1MPa is introduced as protective gas in the whole sintering process.
And (3) putting the sintered blank into a hot isostatic pressing furnace, introducing Ar gas, keeping the temperature at 1000 ℃, the pressure at 200MPa and the heat and pressure for 1h to obtain the high-strength and high-toughness active tungsten alloy.
Example 3
A high-toughness active tungsten alloy comprises the following components in percentage by mass: the preparation process comprises the following steps of (1) 60% of W, 10% of Ti, 10% of Nb and 20% of Zr:
putting W powder with the average particle size of 3 mu m, Ti powder with the average particle size of 8 mu m and Nb powder with the average particle size of 8 mu m into a ball milling tank, wherein the mass of the W powder is 60g, the mass of the Ti powder is 10g and the mass of the Nb powder is 10 g; mixing powder by adopting a high-energy ball milling method, injecting alcohol into a ball milling tank, wherein the alcohol liquid level is 2cm higher than that of the powder, then installing the ball milling tank on a planetary ball mill for ball milling, wherein the ball-material ratio is 1:1, the ball milling rotation speed is 200r/min, and the ball milling time is 16h to obtain a liquid material; and (3) putting the liquid material into a suction filter funnel for suction filtration, and then putting the solid substance obtained by suction filtration into a vacuum drying oven for drying at the drying temperature of 60 ℃ for 24 hours to obtain the inactive mixed powder.
Placing the inactive mixed powder and Zr powder with the average particle size of 10 mu m into a ball milling tank, wherein the mass of the inactive mixed powder is 80g, and the mass of the Zr powder is 20 g; and (3) mounting the ball milling tank on a planetary ball mill for ball milling, wherein the ball-material ratio is 3:1, the ball milling rotation speed is 200r/min, and the ball milling time is 6h, so as to obtain the mixed powder.
And placing the mixed powder into a rubber mold, and performing cold isostatic pressing molding under the pressure of 350MPa for 40min to obtain a green body.
And (2) placing the green body in a sintering furnace for step-by-step pressureless sintering, wherein the process comprises the following steps: heating from room temperature to 500 ℃ at a heating rate of 10 ℃/min, and keeping the temperature at 500 ℃ for 0.5 h; heating from 500 ℃ to 800 ℃ at a heating rate of 3 ℃/min, and keeping the temperature at 800 ℃ for 1 h; heating from 800 ℃ to 1500 ℃ at the heating rate of 2 ℃/min and preserving heat for 3 h; finally, cooling to room temperature along with the furnace to obtain a sintered blank; ar gas of 0.1MPa is introduced as protective gas in the whole sintering process.
And (3) putting the sintered blank into a hot isostatic pressing furnace, introducing Ar gas, keeping the temperature at 1000 ℃, the pressure at 200MPa and the heat and pressure for 1h to obtain the high-strength and high-toughness active tungsten alloy.
Example 4
A high-toughness active tungsten alloy comprises the following components in percentage by mass: the preparation process comprises the following steps of (1) 60% of W, 10% of Ti, 10% of Nb and 20% of Hf:
putting W powder with the average particle size of 3 mu m, Ti powder with the average particle size of 8 mu m and Nb powder with the average particle size of 8 mu m into a ball milling tank, wherein the mass of the W powder is 60g, the mass of the Ti powder is 10g and the mass of the Nb powder is 10 g; mixing powder by adopting a high-energy ball milling method, injecting alcohol into a ball milling tank, wherein the alcohol liquid level is 2cm higher than that of the powder, then installing the ball milling tank on a planetary ball mill for ball milling, wherein the ball-material ratio is 1:1, the ball milling rotation speed is 200r/min, and the ball milling time is 16h to obtain a liquid material; and (3) putting the liquid material into a suction filter funnel for suction filtration, and then putting the solid substance obtained by suction filtration into a vacuum drying oven for drying at the drying temperature of 60 ℃ for 24 hours to obtain the inactive mixed powder.
Placing the inactive mixed powder and Hf powder with the average particle size of 20 mu m into a ball milling tank, wherein the mass of the inactive mixed powder is 80g, and the mass of the Hf powder is 20 g; and (3) mounting the ball milling tank on a planetary ball mill for ball milling, wherein the ball-material ratio is 3:1, the ball milling rotation speed is 200r/min, and the ball milling time is 6h, so as to obtain the mixed powder.
And placing the mixed powder into a rubber mold, and performing cold isostatic pressing molding under the pressure of 350MPa for 40min to obtain a green body.
And (2) placing the green body in a sintering furnace for step-by-step pressureless sintering, wherein the process comprises the following steps: heating from room temperature to 500 ℃ at the heating rate of 5 ℃/min, and keeping the temperature at 500 ℃ for 0.5 h; heating from 500 ℃ to 800 ℃ at a heating rate of 1 ℃/min, and keeping the temperature at 800 ℃ for 1 h; heating from 800 ℃ to 1500 ℃ at the heating rate of 3 ℃/min and preserving heat for 3 h; finally, cooling to room temperature along with the furnace to obtain a sintered blank; ar gas of 0.1MPa is introduced as protective gas in the whole sintering process.
And (3) putting the sintered blank into a hot isostatic pressing furnace, introducing Ar gas, keeping the temperature at 1000 ℃, the pressure at 200MPa and the heat and pressure for 1h to obtain the high-strength and high-toughness active tungsten alloy.
Example 5
A high-toughness active tungsten alloy comprises the following components in percentage by mass: the W is 70%, the Nb is 20%, the Hf is 10%, and the preparation process comprises the following steps:
putting W powder with the average particle size of 3 mu m and Nb powder with the average particle size of 8 mu m into a ball milling tank, wherein the mass of the W powder is 70g, and the mass of the Nb powder is 20 g; mixing powder by adopting a high-energy ball milling method, injecting alcohol into a ball milling tank, wherein the alcohol liquid level is 2cm higher than that of the powder, then installing the ball milling tank on a planetary ball mill for ball milling, wherein the ball-material ratio is 1:1, the ball milling rotation speed is 200r/min, and the ball milling time is 16h to obtain a liquid material; and (3) putting the liquid material into a suction filter funnel for suction filtration, and then putting the solid substance obtained by suction filtration into a vacuum drying oven for drying at the drying temperature of 60 ℃ for 24 hours to obtain the inactive mixed powder.
Placing the inactive mixed powder and Hf powder with the average particle size of 10 mu m into a ball milling tank, wherein the mass of the inactive mixed powder is 90g, and the mass of the Hf powder is 10 g; and (3) mounting the ball milling tank on a planetary ball mill for ball milling, wherein the ball-material ratio is 3:1, the ball milling rotation speed is 200r/min, and the ball milling time is 6h, so as to obtain the mixed powder.
And placing the mixed powder into a rubber mold, and performing cold isostatic pressing molding under the pressure of 350MPa for 40min to obtain a green body.
And (2) placing the green body in a sintering furnace for step-by-step pressureless sintering, wherein the process comprises the following steps: heating from room temperature to 500 ℃ at the heating rate of 7 ℃/min, and keeping the temperature at 500 ℃ for 0.5 h; heating from 500 ℃ to 800 ℃ at a heating rate of 1 ℃/min, and keeping the temperature at 800 ℃ for 1 h; heating from 800 ℃ to 1500 ℃ at the heating rate of 1 ℃/min and preserving heat for 3 h; finally, cooling to room temperature along with the furnace to obtain a sintered blank; ar gas of 0.1MPa is introduced as protective gas in the whole sintering process.
And (3) putting the sintered blank into a hot isostatic pressing furnace, introducing Ar gas, keeping the temperature at 1000 ℃, the pressure at 200MPa and the heat and pressure for 1h to obtain the high-strength and high-toughness active tungsten alloy.
Test example 1
The microstructure photo of the high-toughness active tungsten alloy prepared in the embodiment 1 is shown in fig. 1, and as can be seen from fig. 1, the alloy phase structure of the high-toughness active tungsten alloy prepared in the invention is uniformly distributed, a large-area single-phase agglomeration phenomenon is avoided, and the high-toughness active tungsten alloy is beneficial to obtaining good strength and plasticity of an active W alloy.
Test example 2
The compressive stress-strain curve of the high-toughness active tungsten alloy prepared in the examples 1 to 5 is shown in fig. 2, and specific numerical values are shown in table 1.
TABLE 1 Performance results for high toughness activated tungsten alloys prepared in examples 1-5
Compressive strength (MPa) Critical strain to failure (%) Density (%)
Example 1 2070 10.05 100
Example 2 2160 10.1 99
Example 3 2070 7.6 100
Example 4 1929 8.5 98
Example 5 1951 8.2 100
In Table 1, the compressive strength and the critical failure strain are obtained by a quasi-static compression method, and the reference standard is GB/T7314-2017; the density is obtained by detection with an Archimedes drainage method, and the reference standard is GB/T3850-2015.
As can be seen from fig. 2 and table 1, the phase distribution of the active tungsten alloy prepared by the two-step powder mixing method is uniform, and the tungsten alloy prepared by the method has a plastic platform in the quasi-static compression process, so that the combination of high strength and good plasticity is successfully realized.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A method for controlling the phase distribution uniformity of high-toughness active tungsten alloy is characterized by comprising the following steps:
wet mixing W powder and solid solution metal powder, and removing the solvent in the obtained liquid material to obtain inactive mixed powder; the solid solution metal powder comprises one or more of Ta powder, Nb powder and Ti powder;
dry-mixing the inactive mixed powder and the active powder to obtain mixed powder; the active powder comprises Zr powder, Hf powder and ZrH2Powder HfH2One or more of the powders;
carrying out cold isostatic pressing on the mixed powder to obtain a green body;
sintering the green body to obtain a sintered body;
and carrying out hot isostatic pressing on the sintered blank to obtain the high-strength and high-toughness active tungsten alloy.
2. The method according to claim 1, wherein the average particle diameter of the W powder is 3 to 25 μm; the average grain diameter of the solid-solution metal powder is 5-45 mu m; the average particle size of the active powder is 5-40 μm.
3. The method according to claim 1, wherein the mass ratio of the W powder to the solid-solution metal powder is 20 to 80:5 to 50.
4. The method according to claim 1 or 3, wherein the mass ratio of the inactive mixed powder to the active powder is 40 to 95:5 to 60.
5. The method according to claim 1, wherein the cold isostatic pressing is performed at a pressure of 150 to 400MPa and a dwell time of 10 to 60 min.
6. The method of controlling the uniformity of phase distribution according to claim 1, wherein the sintering is a fractional pressureless sintering; the sintering procedure comprises: heating the mixture from room temperature to 500 ℃, and keeping the temperature for 0.5-2 h; raising the temperature from 500 ℃ to 800 ℃ and preserving the heat for 1-5 h; raising the temperature from 800 ℃ to 1300-1700 ℃, and preserving the heat for 2-5 h.
7. The method of claim 6, wherein the sintering is performed under vacuum or protective atmosphere conditions.
8. The method for controlling the uniformity of phase distribution according to claim 1, wherein the hot isostatic pressing is performed at a pressure of 100 to 200MPa, a temperature of 800 to 1400 ℃ and a holding pressure time of 0.5 to 2 hours.
9. The method for controlling the uniformity of phase distribution according to claim 1, wherein the solvent used in the wet mixing is alcohol; the wet mixing mode comprises ball milling mixing, V-shaped mixing, double cone mixing, three-dimensional mixing or double motion mixing.
10. The method of controlling the uniformity of phase distribution according to claim 1 or 9, wherein the removing the solvent from the liquid material comprises: carrying out suction filtration on the liquid material to obtain a solid substance; the resulting solid material was dried.
CN202110717474.8A 2021-06-28 2021-06-28 Phase distribution uniformity control method of high-toughness active tungsten alloy Active CN113430439B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110717474.8A CN113430439B (en) 2021-06-28 2021-06-28 Phase distribution uniformity control method of high-toughness active tungsten alloy

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110717474.8A CN113430439B (en) 2021-06-28 2021-06-28 Phase distribution uniformity control method of high-toughness active tungsten alloy

Publications (2)

Publication Number Publication Date
CN113430439A true CN113430439A (en) 2021-09-24
CN113430439B CN113430439B (en) 2022-03-01

Family

ID=77754867

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110717474.8A Active CN113430439B (en) 2021-06-28 2021-06-28 Phase distribution uniformity control method of high-toughness active tungsten alloy

Country Status (1)

Country Link
CN (1) CN113430439B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114395707A (en) * 2022-01-07 2022-04-26 合肥工业大学 WTa alloy and preparation method thereof
CN115369299A (en) * 2022-08-19 2022-11-22 北京理工大学 High-specific-gravity energy-containing two-phase high-entropy alloy and preparation method thereof

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1288968A (en) * 1999-09-17 2001-03-28 哈尔滨工业大学 Preparation of zirconium carbide particle-reinforced composite tungsten material
CN101235472A (en) * 2007-11-15 2008-08-06 北京航空航天大学 Zirconium-base amorphous-crystal multiple phase material and preparation method thereof
CN102492884A (en) * 2011-12-07 2012-06-13 北京理工大学 Preparation method of novel tungsten-copper-zinc alloy material
US20160196925A1 (en) * 2013-08-30 2016-07-07 Showa Denko K.K. Tungsten powder and anode body of capacitor
US20200013598A1 (en) * 2010-06-30 2020-01-09 H.C. Starck Inc. Molybdenum containing targets
US20210060653A1 (en) * 2016-12-09 2021-03-04 Michael T. Stawovy Tungsten heavy metal alloy powders and methods of forming them
CN112828298A (en) * 2020-12-31 2021-05-25 中国人民解放军空军工程大学 Preparation method of high-temperature molybdenum alloy spherical powder

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1288968A (en) * 1999-09-17 2001-03-28 哈尔滨工业大学 Preparation of zirconium carbide particle-reinforced composite tungsten material
CN101235472A (en) * 2007-11-15 2008-08-06 北京航空航天大学 Zirconium-base amorphous-crystal multiple phase material and preparation method thereof
US20200013598A1 (en) * 2010-06-30 2020-01-09 H.C. Starck Inc. Molybdenum containing targets
CN102492884A (en) * 2011-12-07 2012-06-13 北京理工大学 Preparation method of novel tungsten-copper-zinc alloy material
US20160196925A1 (en) * 2013-08-30 2016-07-07 Showa Denko K.K. Tungsten powder and anode body of capacitor
US20210060653A1 (en) * 2016-12-09 2021-03-04 Michael T. Stawovy Tungsten heavy metal alloy powders and methods of forming them
CN112828298A (en) * 2020-12-31 2021-05-25 中国人民解放军空军工程大学 Preparation method of high-temperature molybdenum alloy spherical powder

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114395707A (en) * 2022-01-07 2022-04-26 合肥工业大学 WTa alloy and preparation method thereof
CN115369299A (en) * 2022-08-19 2022-11-22 北京理工大学 High-specific-gravity energy-containing two-phase high-entropy alloy and preparation method thereof
CN115369299B (en) * 2022-08-19 2024-04-16 北京理工大学 High-specific gravity energy-containing dual-phase high-entropy alloy and preparation method thereof

Also Published As

Publication number Publication date
CN113430439B (en) 2022-03-01

Similar Documents

Publication Publication Date Title
CN110935878B (en) Injection molding method of titanium alloy part
CN113430439B (en) Phase distribution uniformity control method of high-toughness active tungsten alloy
CN104313380A (en) Method for preparing high density nanocrystalline hard alloy by step sintering
CN107824784B (en) preparation method of light high-strength high-damping porous nickel-titanium shape memory alloy
CN112695262B (en) Titanium alloy-based composite material with micro-structure and preparation method thereof
CN112662903B (en) Preparation method of high-strength Zr-Ti-based alloy
CN101439884A (en) Preparation of FeAl intermetallic compound porous material
CN104674098B (en) Cermet material based on TiCN-(Ti,M)CN core mixed structure and preparation method thereof
CN114635069A (en) High-strength-toughness medium-entropy alloy binding phase Ti (C, N) -based metal ceramic and preparation method thereof
CN109207762A (en) A method of tungsten molybdenum copper composite material is prepared with microwave sintering
CN111254304B (en) Preparation method of in-situ synthesized titanium-nickel alloy framework reinforced titanium-based composite material
CN113354407A (en) Variable-temperature fast-sintering process of aluminum-doped zinc oxide target material
CN113134612A (en) Method for preparing superfine high-purity high-solid-solubility tungsten-based alloy powder
CN103938005A (en) Method for preparing ultra-fine grained titanium and titanium alloy from jet-milled titanium hydride powder
CN114058893B (en) WC-Y with AlCoCrFeNi as binder 2 O 3 -ZrO 2 Preparation method of matrix hard alloy
CN115044794A (en) Cu- (Y) with excellent performance 2 O 3 -HfO 2 ) Alloy and preparation method thereof
CN111203531B (en) Powder metallurgy normal-pressure multi-step sintering method of high-density Ti-Nb-Mo alloy
CN110564989B (en) Preparation method of high-performance Ti-555 type titanium alloy-based composite material
CN110983152B (en) Fe-Mn-Si-Cr-Ni based shape memory alloy and preparation method thereof
CN111621659A (en) Method for preparing Ti2AlNb alloy by powder metallurgy method
CN112897988B (en) Polyvinyl butyral solution bonded lead oxide ceramic for solid oxygen control and preparation method thereof
CN112609106A (en) Zr-Ti-Nb alloy and preparation method thereof
CN114907129A (en) Preparation method of low-dielectric-constant and high-strength silicon nitride
CN113444949A (en) High-density W-Ta-Nb series refractory solid solution alloy and preparation method thereof
CN111893358A (en) CoCrNiCuFeAl/(W, Ti) (C, N) cermet material and preparation method thereof

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
GR01 Patent grant
GR01 Patent grant