Tungsten alloy preparation method based on multi-element doping and wet ball-milling mixing

Abstract

The invention discloses a tungsten alloy preparation method based on multi-element doping and wet ball-milling mixing, and relates to the technical field of powder metallurgy. The method comprises the following steps: weighing tungsten trioxide powder, nickel oxide powder and ferric oxide powder in proportion, and adding an isopropanol solvent for wet ball milling to obtain original slurry; carrying out ball material separation and drying on the original slurry, and fully reducing by using hydrogen to obtain W-Ni-Fe composite powder; multiple elements are doped in the W-Ni-Fe composite powder for secondary material mixing, and multi-element doped mixed powder is obtained; the multi-element doped mixed powder is put into a rubber sleeve and then subjected to cold isostatic pressing, and a W-Ni-Fe alloy bar blank is obtained; and the W-Ni-Fe alloy bar blank is subjected to sintering and vacuum annealing, and the W-Ni-Fe alloy is obtained. According to the embodiment of the invention, the problem that the raw material powder is difficult to mix uniformly in the dry mixing process is solved, and the distribution uniformity of Ni, Fe and doped elements in the multi-element doped mixed powder is improved.

Description

Technical Field

[0001] The present application belongs to the technical field of powder metallurgy, and in particular relates to a method for preparing tungsten alloy based on multi-element doping and wet ball milling mixing. Background Art

[0002] Since tungsten has many advantages such as high melting point, high density, high hardness, high thermal conductivity, low thermal expansion coefficient, and no pollution, it has become the first choice for armor-piercing projectile core materials. High-density tungsten alloy (WHA) has been used as a core material for kinetic energy armor-piercing projectiles. With the continuous development of armor technology, the requirements for the power of armor-piercing projectiles are getting higher and higher. In order to cope with the rapid development of international military armor, and at the same time meet the domestic demand for high-strength, high-toughness, and high-density W-Ni-Fe alloy materials with excellent comprehensive performance. Therefore, the development of high-density tungsten alloy materials has become the focus of the field of powder metallurgy technology. At present, high-density tungsten alloy materials are widely used in aerospace, aviation, military, oil drilling, electrical instruments, medicine and other industrial fields.

[0003] In response to the great demand for high-performance tungsten alloy materials in China, enterprises and research institutes have conducted a lot of research. For example, the patent with publication number CN202011362006 adopts a preparation technology through mixing, cold isostatic pressing, activation and sintering in the same furnace to finally obtain high-tungsten alloy and low-tungsten alloy; the patent with publication number CN104313377A prepares modified tungsten powder and nanocrystalline nickel-iron solid solution by ball milling the raw tungsten powder, nickel powder and iron powder respectively, and then mixes the powder according to the mass ratio of 93:7, and performs processes such as pressing and liquid phase sintering to prepare sintered blanks; The patent with publication number CN201610003039.8 dissolves ammonium metatungstate (AMT) and zirconium nitrate in water, dries, calcines and reduces to obtain composite tungsten powder, mixes nickel powder and iron powder and ball-mills to obtain nickel-iron solid solution, and finally mixes the two powders, presses and sinters to obtain tungsten alloy material; the patent with publication number CN113881881A uses reduced tungsten powder, carbonyl nickel powder and carbonyl iron powder as main raw materials, adds reduced cobalt powder and nano zirconium oxide as doping raw materials, and prepares high specific gravity tungsten alloy material by mixing, pressing and liquid phase sintering.

[0004] The above methods generally adopt the traditional mixing method, the main disadvantages of which are poor powder mixing uniformity, serious chemical composition segregation or complicated operation procedures, which lead to reduced mechanical properties of tungsten alloy materials and make it difficult to meet production needs. Summary of the invention

[0005] The purpose of the present application is to provide a tungsten alloy preparation method based on multi-element doping and wet ball milling mixing, wherein tungsten trioxide, nickel oxide and ferric oxide powders are mixed with isopropyl alcohol solvent and ball milled into an original slurry, and then the ball materials are separated and dried, and fully reduced with hydrogen, and then doped with multiple elements to prepare a multi-element doped mixed powder, thereby overcoming the problem that the raw material powders are difficult to mix uniformly during the dry mixing process and improving the distribution uniformity of Ni, Fe and doping elements in the multi-element doped mixed powder.

[0006] In order to achieve the above objectives, the solution of this application is: The present application embodiment provides a tungsten alloy preparation method based on multi-element doping and wet ball milling mixing, comprising: Weigh tungsten trioxide, nickel oxide and ferric oxide powders in proportion, and add 5% to 15% of the total weight of tungsten trioxide, nickel oxide and ferric oxide powders in isopropanol solvent for wet ball milling to obtain an original slurry, wherein the ratio of tungsten trioxide: nickel oxide: ferric oxide powder is 85:5:10; The original slurry is subjected to ball material separation and drying, and fully reduced with hydrogen to obtain W-Ni-Fe composite powder; 0.2% to 1.0% of cobalt powder, 0.05% to 0.1% of manganese powder, 0.2% to 1.5% of rhenium powder and 1.0% to 3.0% of molybdenum powder are added to the W-Ni-Fe composite powder, based on the total weight of the W-Ni-Fe composite powder, and secondary mixing is performed to obtain a multi-element doped mixed powder; The multi-element doped mixed powder is placed in a rubber sleeve and then cold isostatically pressed to obtain a W-Ni-Fe alloy rod blank; The W-Ni-Fe alloy rod blank is sintered and vacuum annealed to obtain the W-Ni-Fe alloy.

[0007] According to the above method of the embodiment of the present application, the following additional technical features may also be provided: Furthermore, the ball milling parameters of the wet ball milling include: a ball-to-material ratio of 3:1, a ball milling speed of 160 to 200 r / min, a ball milling time of 5 to 10 h, and a ball milling medium of stainless steel balls.

[0008] Further, the original slurry is subjected to ball separation and drying, and is fully reduced with hydrogen to obtain W-Ni-Fe composite powder, including: The stainless steel balls were separated from the original slurry through a sieve and dried in an oven at 80°C for 12 h.

[0009] Further, hydrogen is used for full reduction to obtain W-Ni-Fe composite powder, including: The original slurry after ball separation and drying is fully reduced in a hydrogen atmosphere, and the reduction parameters include a reduction temperature of 700° C. to 900° C. and a reduction time of 2 to 6 hours.

[0010] Furthermore, the secondary mixing time is 3 to 6 hours.

[0011] Furthermore, the pressing pressure of the cold isostatic pressing is 160 to 240 MPa, and the holding time is 2 to 6 minutes.

[0012] Furthermore, the sintering temperature is 1450° C. to 1500° C., and the holding time is 1 to 3 hours.

[0013] Furthermore, the vacuum degree of vacuum annealing is not less than 9.6×10 -2 Pa, the vacuum annealing temperature is 1100°C to 1250°C, and the annealing time is 1 to 4 hours.

[0014] The tungsten alloy preparation method based on multi-element doping and wet ball milling mixing provided in the embodiment of the present application has the following beneficial technical effects compared with the prior art: In the embodiment of the present application, tungsten trioxide, nickel oxide and ferric oxide powders are fully mixed by wet ball milling to form a uniform original slurry. This uniform mixing helps to form a uniform W-Ni-Fe composite powder in the subsequent reduction and compounding process, thereby improving the composition uniformity and comprehensive performance of the final W-Ni-Fe alloy.

[0015] The W-Ni-Fe composite powder obtained by ball separation, drying and hydrogen reduction of the original slurry in the embodiment of the present application is further mixed with cobalt powder, manganese powder, rhenium powder and molybdenum powder for secondary mixing, which improves the wettability of the binder phase to the W particles, is conducive to obtaining a microstructure with uniform tissue distribution, and improves the interface strength between W and the binder phase to meet specific application requirements.

[0016] The wet ball milling parameters, reduction parameters, secondary mixing time, cold isostatic pressing parameters, sintering temperature and holding time, and vacuum annealing parameters of the embodiment of the present application are all precisely controlled to ensure the formation of a solid tungsten skeleton, thereby reducing severe deformation of the alloy rod during the sintering process, avoiding machining and other processes, eliminating the negative impact of hydrogen embrittlement on alloy properties, and improving the mechanical properties of tungsten alloy materials.

[0017] The embodiment of the present application uses hydrogen as a reducing agent. Compared with other reducing agents such as carbon or carbon monoxide, hydrogen has higher reduction efficiency and less pollution emissions. In addition, by precisely controlling each link in the preparation process, energy consumption and waste generation can also be reduced, which is in line with the concept of green manufacturing and sustainable development. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 A schematic flow chart of a method for preparing tungsten alloy based on multi-element doping and wet ball milling mixing according to an embodiment of the present application is shown. DETAILED DESCRIPTION

[0019] In order to make the above-mentioned purposes, features and advantages of the present application more obvious and easy to understand, the specific implementation methods of the present application are described in detail below in conjunction with the accompanying drawings. It is to be understood that the specific embodiments described herein are only used to explain the present application, rather than to limit the present application. It should also be noted that, for ease of description, only some structures related to the present application are shown in the accompanying drawings, rather than all structures. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of this application.

[0020] The terms "including" and "having" and any variations thereof in this application are intended to cover non-exclusive inclusions. For example, a process, method, system, product or device comprising a series of steps or units is not limited to the listed steps or units, but may optionally include steps or units not listed, or may optionally include other steps or units inherent to these processes, methods, products or devices.

[0021] Reference to "embodiments" in this application means that a particular feature, structure, or characteristic described in conjunction with the embodiments may be included in at least one embodiment of the present application. The appearance of the phrase in various locations in the specification does not necessarily refer to the same embodiment, nor is it an independent or alternative embodiment that is mutually exclusive with other embodiments. It is explicitly and implicitly understood by those skilled in the art that the embodiments described in this application may be combined with other embodiments.

[0022] like Figure 1 As shown, the embodiment of the present application provides a method for preparing tungsten alloy based on multi-element doping and wet ball milling mixing, comprising the following steps: Step 101, weigh tungsten trioxide, nickel oxide and ferric oxide powders in proportion, and add 5% to 15% of the total weight of tungsten trioxide, nickel oxide and ferric oxide powders of isopropanol solvent for wet ball milling to obtain an original slurry, wherein the ratio of tungsten trioxide: nickel oxide: ferric oxide powder is 85:5:10.

[0023] In the process of preparing W-Ni-Fe alloy, step 101 involves weighing the raw materials in proportion and wet ball milling to obtain the original slurry. The raw materials include tungsten trioxide, nickel oxide and ferric oxide powder. They are weighed in a ratio of 85:5:10, that is, tungsten trioxide accounts for 85%, nickel oxide accounts for 5%, and ferric oxide accounts for 10%. This ratio is selected to obtain a W-Ni-Fe composite powder with specific properties in the subsequent reduction and alloying process.

[0024] The addition of isopropanol solvent is mainly to improve the dispersibility and fluidity of the raw material powder, so that it is easier to form a uniform slurry during the wet ball milling process. The addition amount is 5% to 15% of the total weight of tungsten trioxide, nickel oxide and ferric oxide powder. This range can be adjusted according to specific process requirements and raw material characteristics.

[0025] The raw material powder and isopropanol solvent are mixed evenly by wet ball milling, and the powder particles are refined, laying the foundation for the subsequent reduction and alloying process. The ball-to-material ratio is 3:1, that is, during the ball milling process, the weight ratio of the number of stainless steel balls to the raw material powder is 3:1. This ratio is chosen to ensure that the raw material powder can be refined by sufficient impact force. The ball milling speed is 160 to 200 r / min. The choice of speed will affect the energy input and powder refinement effect during the ball milling process. Within this range, it can be adjusted according to specific equipment and process requirements. The ball milling time is 5 to 10h. The length of the ball milling time will affect the degree of refinement and uniformity of the powder. Within this time range, it can be adjusted according to the raw material characteristics and the target powder particle size. The ball milling medium is stainless steel balls. As ball milling media, stainless steel balls have the advantages of high hardness and good wear resistance, and can effectively refine the raw material powder.

[0026] After the wet ball milling in the above steps, a uniform original slurry can be obtained, which has good dispersibility and fluidity, providing convenience for subsequent processing steps.

[0027] In summary, step 101 obtains high-quality raw slurry by accurately weighing the raw materials, selecting the appropriate amount of isopropanol solvent to be added, and optimizing the wet ball milling parameters, laying a solid foundation for subsequent processing steps.

[0028] Step 102, separating the raw slurry into balls and drying them, and fully reducing them with hydrogen to obtain W-Ni-Fe composite powder.

[0029] In step 101, the original slurry is obtained by wet ball milling, which contains tungsten trioxide, nickel oxide, ferric oxide powder and stainless steel balls (as ball milling media). The purpose of step 102 is to separate the stainless steel balls from the slurry for subsequent processing. This is usually achieved by a screen or other separation equipment to ensure that the stainless steel balls are effectively separated from the powder in the slurry.

[0030] The separated slurry (excluding stainless steel balls) needs to be dried to remove the moisture or solvent (such as isopropyl alcohol) therein. The drying temperature is set to 80°C and the drying time is 12 hours. This temperature and time are selected to ensure that the moisture or solvent in the slurry can be fully evaporated while avoiding adverse effects on the properties of the powder.

[0031] The main components of the dried slurry are a mixture of tungsten trioxide, nickel oxide and ferric oxide. Through hydrogen reduction, these oxides can be reduced to the corresponding metal elements (W, Ni, Fe), thereby forming a W-Ni-Fe composite powder. It is carried out in a hydrogen atmosphere to ensure that the reduction reaction is fully carried out. The reduction temperature is 700℃ to 900℃. This temperature range is selected to ensure that the reduction reaction can be carried out efficiently while avoiding sintering or agglomeration of the powder due to excessive temperature. The reduction time is 2 to 6 hours. This time range is selected to ensure that the reduction reaction can be carried out thoroughly to obtain a high-purity W-Ni-Fe composite powder.

[0032] In summary, step 102 involves multiple steps such as ball separation, drying and hydrogen reduction. By strictly controlling the conditions and parameters of these steps, high-quality W-Ni-Fe composite powder can be obtained, providing a strong guarantee for subsequent alloy preparation.

[0033] Step 103, adding 0.2% to 1.0% of cobalt powder, 0.05% to 0.1% of manganese powder, 0.2% to 1.5% of rhenium powder and 1.0% to 3.0% of molybdenum powder based on the total weight of the W-Ni-Fe composite powder to the W-Ni-Fe composite powder, performing secondary mixing to obtain a multi-element doped mixed powder.

[0034] In the preparation process of W-Ni-Fe alloy, step 103 involves adding specific proportions of cobalt powder, manganese powder, rhenium powder and molybdenum powder to the W-Ni-Fe composite powder, and performing secondary mixing to obtain a multi-element doped mixed powder.

[0035] The addition of cobalt powder can significantly improve the hardness and wear resistance of the alloy, and also help to improve the thermal stability and oxidation resistance of the alloy. Manganese powder can enhance the strength and toughness of the alloy and improve the fatigue resistance of the alloy. Rhenium powder is a high melting point and high density metal. Its addition can significantly improve the melting point, hardness and corrosion resistance of the alloy. The addition of molybdenum powder can further improve the strength and hardness of the alloy, and also help to improve the creep resistance and corrosion resistance of the alloy.

[0036] Specifically, the addition amounts of cobalt powder, manganese powder, rhenium powder and molybdenum powder are controlled to be between 0.2% and 1.0%, 0.05% and 0.1%, 0.2% and 1.5% and 1.0% and 3.0% of the total weight of the W-Ni-Fe composite powder, respectively. These proportions are selected to further optimize the comprehensive performance of the alloy while ensuring its basic properties.

[0037] Secondary mixing is the process of fully mixing the doping elements with the W-Ni-Fe composite powder. This step is usually carried out by mechanical stirring or ball milling to ensure that the doping elements can be evenly distributed in the composite powder. The secondary mixing time is 3 to 6 hours. This time range is selected to ensure sufficient mixing between the doping elements and the composite powder, while avoiding excessive refinement or agglomeration of the powder particles caused by too long mixing.

[0038] After secondary mixing, a multi-element doped mixed powder can be obtained. This powder not only has the basic properties of W-Ni-Fe alloy, but also has higher comprehensive properties such as hardness, wear resistance, strength and corrosion resistance through the introduction of doping elements. These performance improvements enable the multi-element doped mixed powder to form a more dense and uniform alloy structure during subsequent sintering and vacuum annealing.

[0039] In summary, step 103 prepares a multi-element doped mixed powder with excellent comprehensive performance by precisely controlling the ratio of doping elements and the time of secondary mixing, laying a solid foundation for the subsequent sintering and vacuum annealing process of the alloy.

[0040] Step 104, placing the multi-element doped mixed powder into a rubber sleeve and performing cold isostatic pressing to obtain a W-Ni-Fe alloy rod blank.

[0041] The multi-element doped mixed powder obtained after secondary mixing is placed in a rubber sleeve, which not only plays a role of wrapping and fixing, but also provides a certain buffer and protection during the cold isostatic pressing process to prevent the powder from overflowing or being subjected to uneven pressure under high pressure. Subsequently, the rubber sleeve containing the powder is placed in a cold isostatic press, and high pressure is applied to tightly combine the powder particles to form a dense rod blank.

[0042] The "rubber sleeve" mentioned in the embodiment of the present application is an auxiliary tool for loading mixed powder for cold isostatic pressing. The "rubber sleeve" here does not refer to a specific type of rubber sleeve, but a rubber or elastic material sleeve selected according to its use and process requirements, which can meet the requirements of loading powder and bearing the pressure required in the cold isostatic pressing process.

[0043] Specifically, cold isostatic pressing is a molding method that uses liquid to transmit pressure. The powder is loaded into a special mold (the "rubber sleeve" in the embodiment of this application), and then placed in a high-pressure container. High-pressure liquid (usually oil or water) is used as a medium for transmitting pressure to uniformly compress the powder in the mold, thereby obtaining a blank with the desired shape and density.

[0044] Therefore, this "rubber sleeve" needs to have a certain degree of elasticity and sealing to ensure that it will not break or leak under high pressure. At the same time, it must be able to withstand certain temperature changes and chemical corrosion to ensure the smooth progress of the molding process and the quality of the blank.

[0045] In practical applications, the "rubber sleeve" formed by cold isostatic pressing may be made of a variety of materials, such as natural rubber, synthetic rubber, plastic, etc. The specific choice depends on the type of powder, molding temperature, pressure and other process parameters, as well as factors such as cost. In addition, the design of the "rubber sleeve" also needs to consider factors such as its shape, size, wall thickness, etc. to ensure that it matches the mold and high-pressure container of the cold isostatic press to obtain the best molding effect.

[0046] The pressing pressure of cold isostatic pressing is precisely controlled in the range of 160 to 240 MPa. The selection of this pressure range is based on the physical properties of the powder and the required density of the rod blank. Too low a pressure may not allow the powder particles to be fully combined, while too high a pressure may cause the rubber sleeve to rupture or defects inside the rod blank.

[0047] The holding time is set to 2 to 6 minutes. This period of time is enough for the powder particles to fully combine under high pressure to form a stable structure. The length of the holding time has an important influence on the density and uniformity of the final rod blank. Too short a holding time may result in insufficiently combined powder particles inside the rod blank, while too long a holding time may increase production costs and reduce production efficiency.

[0048] Cold isostatic pressing is a key step in the preparation of high-performance alloy materials. It can not only significantly improve the density and strength of the material, but also improve the microstructure and performance of the material. By precisely controlling the pressing pressure and holding time, it can ensure that the final bar billet has uniform density and good mechanical properties, laying a solid foundation for the subsequent sintering and vacuum annealing process.

[0049] In practical applications, factors such as the selection of cold isostatic presses, the material and thickness of the rubber sleeve, the filling density of the powder, and the temperature control during the pressing process need to be considered. These factors will affect the quality and performance of the final billet, so strict control and optimization are required during the preparation process.

[0050] In summary, step 104 ensures that the final bar blank has excellent performance and stability by precisely controlling the pressing pressure and holding time, thus providing reliable protection for the subsequent sintering and vacuum annealing processes.

[0051] Step 105, sintering and vacuum annealing the W-Ni-Fe alloy rod blank to obtain the W-Ni-Fe alloy.

[0052] In the material preparation process, step 105 not only determines the physical and chemical properties of the final product, but also directly affects the performance and application range of the product.

[0053] Sintering is the process of heating a powder or granular material to a temperature range below its melting point to make it bond or solidify, thereby forming a dense, hard solid. For W-Ni-Fe alloy billets, sintering is a key step to make its internal particles tightly bonded to form an alloy with a certain strength and hardness. The sintering temperature is set at 1450℃ to 1500℃. The selection of this temperature range is based on the physical properties of W-Ni-Fe alloy and the principle of sintering kinetics. Within this temperature range, the particles inside the alloy can fully diffuse and rearrange to form a dense microstructure.

[0054] The holding time is set to 1 to 3 hours. The length of the holding time directly affects the degree of sintering. Too short a holding time may lead to incomplete sintering, while too long a holding time may cause excessive growth of the internal structure of the alloy, affecting the performance.

[0055] Vacuum annealing is the process of heating the material in a vacuum or inert gas environment. It is mainly used to eliminate residual stress inside the material, improve the microstructure and enhance performance. The vacuum degree is not less than 9.6×10^-2Pa. High vacuum can effectively prevent the material from reacting with oxygen, nitrogen and other gases in the air during the annealing process, thereby maintaining the purity and performance of the material. The vacuum annealing temperature is set at 1100℃ to 1250℃. This temperature range is selected to ensure that the residual stress inside the alloy is fully released while avoiding the destruction of the alloy structure due to excessively high temperatures. The annealing time is set to 1 to 4 hours. The length of the annealing time also affects the annealing effect. Appropriate annealing time can ensure the full elimination of residual stress and the optimization of the microstructure.

[0056] In summary, step 105 prepares a W-Ni-Fe alloy with excellent performance and stable quality by precisely controlling the sintering temperature and holding time, as well as the vacuum degree, annealing temperature and annealing time during the vacuum annealing process.

[0057] Specifically, in the first embodiment, tungsten trioxide, nickel oxide, ferric oxide powder and isopropanol are weighed in a mass ratio and ball-milled, wherein the tungsten trioxide content is 85%, the nickel oxide content is 5%, the ferric oxide content is 10%, the isopropanol solvent is added in a proportion of 5%, the ball-to-material ratio is 3:1, the ball milling speed is 160r / min, and the ball milling time is 5h to obtain an original slurry; the original slurry is sieved through a sieve, and then dried in an oven at 80°C for 12h, and reduced in a tubular furnace, the hydrogen reduction temperature is 700°C, and the time is 2h to obtain a W-Ni-Fe composite powder; doping elements are added to the W-Ni-Fe composite powder, wherein the cobalt powder contains The content of manganese powder is 0.2%, the content of rhenium powder is 0.05%, the content of rhenium powder is 0.2%, the content of molybdenum powder is 1.0%, and the secondary mixing time is 3h to obtain a multi-element doped mixed powder; the multi-element doped mixed powder is loaded into a rubber sleeve, and pressed by a cold isostatic press to obtain a W-Ni-Fe alloy rod blank, the pressing pressure is 160MPa, and the holding time is 2min; the W-Ni-Fe alloy rod blank is placed in a molybdenum-lanthanum boat covered with alumina sand, sintered in a hydrogen furnace, and then annealed in a vacuum annealing furnace, the sintering process parameters are: temperature 1450℃, time 1h; vacuum annealing parameters are: temperature 1100℃, time 1h, vacuum degree not less than 9.6×10 -2 Pa; The results show that the W-Ni-Fe alloy prepared in this embodiment has a tensile strength of 1098 MPa, an elongation of more than 12%, and an impact toughness value of more than 120 J / cm 2 .

[0058] Specifically, in the second embodiment, tungsten trioxide, nickel oxide, ferric oxide powder and isopropanol are weighed in a mass ratio and ball-milled, wherein the tungsten trioxide content is 85%, the nickel oxide content is 5%, the ferric oxide content is 10%, the isopropanol solvent addition ratio is 10%, the ball-to-material ratio is 3:1, the ball milling speed is 180r / min, and the ball milling time is 8h to obtain an original slurry; the original slurry is sieved through a sieve, and then dried in an oven at 80°C for 12h, and reduced in a tubular furnace, the hydrogen reduction temperature is 700°C, the hydrogen reduction temperature is 800°C, and the time is 4h to obtain a W-Ni-Fe composite powder; doping elements are added to the W-Ni-Fe composite powder, and the The cobalt powder content is 0.6%, the manganese powder content is 0.08%, the rhenium powder content is 0.8%, and the molybdenum powder content is 2.0%. The secondary mixing time is 4.5h to obtain a multi-element doped mixed powder; the multi-element doped mixed powder is loaded into a rubber sleeve, and pressed by a cold isostatic press to obtain a W-Ni-Fe alloy rod blank, the pressing pressure is 200MPa, and the holding time is 4min; the W-Ni-Fe alloy rod blank is placed in a molybdenum-lanthanum boat covered with alumina sand, sintered in a hydrogen furnace, and then annealed in a vacuum annealing furnace, the sintering process parameters are: temperature 1480℃, time 2h; vacuum annealing parameters are: temperature 1180℃, time 2.5h, vacuum degree not less than 9.6×10 -2 Pa; After testing, the W-Ni-Fe alloy prepared in this embodiment has a tensile strength of 1186MPa, an elongation of more than 35%, and an impact toughness value of more than 253J / cm 2 .

[0059] Specifically, in the third embodiment, tungsten trioxide, nickel oxide, ferric oxide powder and isopropanol are weighed in a mass ratio and ball-milled, wherein the tungsten trioxide content is 85%, the nickel oxide content is 5%, the ferric oxide content is 10%, the isopropanol solvent addition ratio is 15%, the ball-to-material ratio is 3:1, the ball milling speed is 200r / min, and the ball milling time is 10h to obtain an original slurry; the original slurry is sieved through a sieve, and then dried in an oven at 80°C for 12h, and reduced in a tubular furnace, the hydrogen reduction temperature is 900°C, and the time is 6h to obtain a W-Ni-Fe composite powder; doping elements are added to the W-Ni-Fe composite powder, wherein cobalt powder The content of W-Ni-Fe alloy rods is 1.0%, the content of manganese powder is 0.1%, the content of rhenium powder is 1.5%, and the content of molybdenum powder is 3.0%. The secondary mixing time is 6h. The multi-element doped mixed powder is obtained. The multi-element doped mixed powder is loaded into a rubber sleeve and pressed by a cold isostatic press to obtain a W-Ni-Fe alloy rod blank. The pressing pressure is 240MPa and the holding time is 6min. The W-Ni-Fe alloy rod blank is placed in a molybdenum-lanthanum boat covered with alumina sand, sintered in a hydrogen furnace, and then annealed in a vacuum annealing furnace. The sintering process parameters are: temperature 1500℃, time 3h; vacuum annealing parameters are: temperature 1250℃, time 4h, vacuum degree not less than 9.6×10 -2 Pa; The W-Ni-Fe alloy prepared in this embodiment has a tensile strength of 1070 MPa, an elongation of more than 23%, and an impact toughness value of more than 160 J / cm 2 .

[0060] The embodiments of the present application are described above in conjunction with the accompanying drawings, but the present application is not limited to the above-mentioned specific implementation methods. The above-mentioned specific implementation methods are merely illustrative and not restrictive. Under the guidance of the present application, ordinary technicians in this field can also make many forms without departing from the purpose of the present application and the scope of protection of the claims, all of which are within the protection of the present application.

Claims

1. A method for preparing tungsten alloy based on multi-element doping and wet ball milling mixing, characterized in that: The method comprises: Weigh tungsten trioxide, nickel oxide and ferric oxide powders in proportion, and add 5% to 15% of the total weight of the tungsten trioxide, nickel oxide and ferric oxide powders to perform wet ball milling to obtain an original slurry, wherein the ratio of tungsten trioxide: nickel oxide: ferric oxide powder is 85:5:10; The original slurry is subjected to ball-material separation and drying, and fully reduced with hydrogen to obtain W-Ni-Fe composite powder; 0.2% to 1.0% of cobalt powder, 0.05% to 0.1% of manganese powder, 0.2% to 1.5% of rhenium powder and 1.0% to 3.0% of molybdenum powder are added to the W-Ni-Fe composite powder, based on the total weight of the W-Ni-Fe composite powder, to perform secondary mixing to obtain a multi-element doped mixed powder; The multi-element doped mixed powder is placed in a rubber sleeve and then isostatically pressed to obtain a W-Ni-Fe alloy rod blank; The W-Ni-Fe alloy rod blank is sintered and vacuum annealed to obtain the W-Ni-Fe alloy.

2. The method for preparing tungsten alloy according to claim 1, wherein: The ball milling parameters of the wet ball milling include: a ball-to-material ratio of 3:1, a ball milling speed of 160 to 200 r / min, a ball milling time of 5 to 10 hours, and a ball milling medium of stainless steel balls.

3. The method for preparing tungsten alloy according to claim 2, wherein: The raw slurry is subjected to ball-material separation and drying, and fully reduced with hydrogen to obtain W-Ni-Fe composite powder, including: The stainless steel balls were separated from the original slurry through a sieve and dried in an oven at 80° C. for 12 h.

4. The method for preparing tungsten alloy according to claim 1 or 3, characterized in that: The method of fully reducing with hydrogen to obtain W-Ni-Fe composite powder comprises: The original slurry after ball separation and drying is fully reduced in a hydrogen atmosphere, and the reduction parameters include a reduction temperature of 700° C. to 900° C. and a reduction time of 2 to 6 hours.

5. The method for preparing tungsten alloy according to claim 1, wherein: The secondary mixing time is 3 to 6 hours.

6. The method for preparing tungsten alloy according to claim 1, characterized in that: The pressing pressure of the cold isostatic pressing is 160 to 240 MPa, and the holding time is 2 to 6 minutes.

7. The method for preparing tungsten alloy according to claim 1, characterized in that: The sintering temperature is 1450° C. to 1500° C., and the holding time is 1 to 3 hours.

8. The method for preparing tungsten alloy according to claim 1, wherein: The vacuum degree of the vacuum annealing is not less than 9.6×10 -2 Pa, the vacuum annealing temperature is 1100°C to 1250°C, and the annealing time is 1 to 4 hours.

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