CN115404419A - Preparation method of tungsten filament reinforced tungsten-based composite material - Google Patents
Preparation method of tungsten filament reinforced tungsten-based composite material Download PDFInfo
- Publication number
- CN115404419A CN115404419A CN202211144036.8A CN202211144036A CN115404419A CN 115404419 A CN115404419 A CN 115404419A CN 202211144036 A CN202211144036 A CN 202211144036A CN 115404419 A CN115404419 A CN 115404419A
- Authority
- CN
- China
- Prior art keywords
- tungsten
- dimensional
- temperature
- based composite
- composite material
- 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
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C47/00—Making alloys containing metallic or non-metallic fibres or filaments
- C22C47/14—Making alloys containing metallic or non-metallic fibres or filaments by powder metallurgy, i.e. by processing mixtures of metal powder and fibres or filaments
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
- B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C47/00—Making alloys containing metallic or non-metallic fibres or filaments
- C22C47/02—Pretreatment of the fibres or filaments
- C22C47/04—Pretreatment of the fibres or filaments by coating, e.g. with a protective or activated covering
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C47/00—Making alloys containing metallic or non-metallic fibres or filaments
- C22C47/02—Pretreatment of the fibres or filaments
- C22C47/06—Pretreatment of the fibres or filaments by forming the fibres or filaments into a preformed structure, e.g. using a temporary binder to form a mat-like element
- C22C47/062—Pretreatment of the fibres or filaments by forming the fibres or filaments into a preformed structure, e.g. using a temporary binder to form a mat-like element from wires or filaments only
- C22C47/066—Weaving wires
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C49/00—Alloys containing metallic or non-metallic fibres or filaments
- C22C49/02—Alloys containing metallic or non-metallic fibres or filaments characterised by the matrix material
- C22C49/10—Refractory metals
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C49/00—Alloys containing metallic or non-metallic fibres or filaments
- C22C49/14—Alloys containing metallic or non-metallic fibres or filaments characterised by the fibres or filaments
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
- C23C16/08—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metal halides
- C23C16/14—Deposition of only one other metal element
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E30/00—Energy generation of nuclear origin
- Y02E30/10—Nuclear fusion reactors
Abstract
The invention provides a preparation method of a tungsten filament reinforced tungsten-based composite material, which comprises the following steps: a) Carrying out chemical vapor deposition on the three-dimensional tungsten wire braided body to obtain a three-dimensional tungsten wire braided body compounded with a tungsten coating; b) Dipping the three-dimensional tungsten wire braided body obtained in the step A) in tungsten powder slurry, then sequentially drying and presintering to obtain a three-dimensional tungsten wire braided body filled with tungsten materials, and repeating the step for multiple times; c) Dipping the three-dimensional tungsten wire braid filled with the tungsten material obtained in the step B) in tungstate dipping solution, then sequentially calcining, reducing and presintering to obtain a presintered body, and repeating the step for multiple times; d) And C), sequentially sintering and pressure processing the pre-sintered body obtained in the step C) to obtain the tungsten filament reinforced tungsten-based composite material. The tungsten filament reinforced tungsten-based composite material prepared by the method provided by the application has excellent room-temperature three-dimensional strength and room-temperature three-dimensional toughness.
Description
Technical Field
The invention relates to the technical field of tungsten-based materials, in particular to a preparation method of a tungsten filament reinforced tungsten-based composite material.
Background
Tungsten has the advantages of high melting point, low sputtering rate and the like, and is one of the most potential surface wall materials in a fusion reactor device in the future. However, the traditional tungsten material has high ductile-brittle transition temperature and brittleness (usually expressed as elongation after fracture < 3%) at room temperature, and is easy to crack after being heated and cooled for many times; the tungsten material is recrystallized after long-time high-temperature service, the ductile-brittle transition temperature of the tungsten material is further increased, and the tungsten material is more prone to cracking under the same service condition.
The method for improving the room temperature brittleness of the tungsten material mainly comprises the steps of refining the grain size, adding alloy elements for solid solution strengthening or adding second phase particles for dispersion strengthening and the like. Research in recent years has shown that: by adding metal or non-metal fibers into the tungsten matrix, the shear band can be prevented from diffusing, new shear bands can be promoted to proliferate, the brittle material has higher toughness while keeping the strength, and therefore, the fiber toughened tungsten material is feasible to improve the room-temperature brittleness.
Chinese patent publication No. CN 112442643B discloses a laminated fiber toughened tungsten-based composite material and a preparation method thereof, the composite material comprises a tungsten substrate layer, a titanium foil and a tungsten fiber mesh toughened layer which are alternately laminated with each other, tungsten powder, the tungsten fiber mesh and the titanium foil which are subjected to high-energy ball milling treatment are alternately laminated and put into a mold, and discharge plasma sintering is performed under a vacuum condition to prepare the laminated fiber toughened tungsten-based composite material. The method adopts the layered fiber to toughen the tungsten-based material, and although the toughness in all directions in the plane of the layered fiber is obviously improved, the toughening effect in the interlayer direction is almost not achieved.
Disclosure of Invention
The invention aims to provide a preparation method of a tungsten wire reinforced tungsten-based composite material, and the preparation method provided by the application can be used for preparing the tungsten wire reinforced tungsten-based composite material with excellent room-temperature three-dimensional strength and room-temperature three-dimensional toughness.
In view of this, the present application provides a method for preparing a tungsten filament reinforced tungsten-based composite material, comprising the following steps:
a) Carrying out chemical vapor deposition on the three-dimensional tungsten wire braided body to obtain a three-dimensional tungsten wire braided body compounded with a tungsten coating;
b) Dipping the three-dimensional tungsten wire braided body compounded with the tungsten coating obtained in the step A) in tungsten powder slurry, and then sequentially drying and presintering to obtain a three-dimensional tungsten wire braided body filled with tungsten materials; repeating for multiple times;
c) Dipping the three-dimensional tungsten wire braid filled with the tungsten material obtained in the step B) in tungstate dipping solution, sequentially calcining, reducing and presintering to obtain a presintered body, and repeating the step for multiple times;
d) And C), sequentially sintering and pressure processing the pre-sintered body obtained in the step C) to obtain the tungsten filament reinforced tungsten-based composite material.
Preferably, in the step A), the diameter of the tungsten wire adopted in the three-dimensional tungsten wire knitted body is 20-500 μm, and the purity of the tungsten wire is more than 99.99%;
preferably, the tungsten wire is further doped with one or more of potassium, rhenium and rare earth oxides.
Preferably, in the step a), the volume ratio of the tungsten filament in the three-dimensional tungsten filament woven body is 2 to 40%.
Preferably, in step a), the chemical vapor deposition is performed by using raw materials with a volume ratio of 1: 2-1, 4, and hydrogen, wherein the temperature of the chemical vapor deposition is 400-600 ℃, and the pressure is 10-100 kPa.
Preferably, in the step B), the tungsten powder slurry comprises tungsten powder and absolute ethyl alcohol, the particle size of the tungsten powder is 0.5-5 μm, and the mass content of the tungsten powder is 60-95%.
Preferably, in the step B), the pre-sintering atmosphere is a hydrogen atmosphere, and the pre-sintering temperature is 1200 to 1600 ℃.
Preferably, the step B) is repeated 4 times or more, and the relative density of the three-dimensional tungsten filament woven body filled with the tungsten material is 60% or more.
Preferably, in step C), the tungstate is ammonium metatungstate, and the mass concentration of the tungstate impregnation liquid is 50 to 95%.
Preferably, in the step C), the calcination is carried out in an air atmosphere, and the calcination temperature is 600-1000 ℃; the reducing atmosphere is hydrogen atmosphere, and the reducing temperature is 700-900 ℃; the presintering atmosphere is hydrogen atmosphere, and the presintering temperature is 1200-1600 ℃;
preferably, step C) is repeated 4 or more times, the relative density of the pre-sintered body being 70% or more.
Preferably, in the step D), the sintering is carried out in a hydrogen atmosphere, and the sintering temperature is 1600-2000 ℃;
preferably, in the step D), the pressure processing mode is forging, the forging temperature is 1200-1700 ℃, and the deformation is 20-95%;
preferably, in step D), the sintered body obtained by the sintering has a relative density of 90% or more.
The application provides a preparation method of a tungsten filament reinforced tungsten-based composite material, which utilizes a tungsten filament three-dimensional woven body as a reinforcement, sequentially carries out chemical vapor deposition, tungsten powder slurry filling and tungstate dipping reduction to fill tungsten materials into pores in the reinforcement, and finally carries out sintering and pressure processing to obtain the tungsten filament reinforced tungsten-based composite material. In the preparation process of the tungsten filament reinforced tungsten-based composite material, the tungsten filament reinforced tungsten-based composite material is prepared by adopting a method of combining a chemical vapor deposition method, tungsten powder slurry filling and tungstate dipping reduction, so that the tungsten filament three-dimensional woven body is filled and densified, and then the tungsten filament reinforced tungsten-based composite material is prepared by sintering and pressure processing, so that the tungsten filament reinforced tungsten-based composite material with excellent room-temperature three-dimensional strength and room-temperature three-dimensional toughness is obtained.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
The application provides a preparation method of a tungsten filament reinforced tungsten-based composite material, which combines chemical vapor deposition, tungsten powder slurry filling and tungstate impregnation, so that the obtained tungsten filament reinforced tungsten-based composite material has the advantages of the traditional tungsten material, and also has the characteristics of excellent room-temperature three-dimensional strength and room-temperature three-dimensional toughness. Specifically, the embodiment of the invention discloses a preparation method of a tungsten filament reinforced tungsten-based composite material, which comprises the following steps:
a) Carrying out chemical vapor deposition on the three-dimensional tungsten wire braided body to obtain a three-dimensional tungsten wire braided body compounded with a tungsten coating;
b) Dipping the three-dimensional tungsten wire braided body compounded with the tungsten coating obtained in the step A) in tungsten powder slurry, and then sequentially drying and presintering to obtain a three-dimensional tungsten wire braided body filled with tungsten materials; repeating for multiple times;
c) Dipping the three-dimensional tungsten wire braid filled with the tungsten material obtained in the step B) in tungstate dipping solution, then sequentially calcining, reducing and presintering to obtain a presintered body, and repeating the step for multiple times;
d) And C), sequentially sintering and pressure processing the pre-sintered body obtained in the step C) to obtain the tungsten filament reinforced tungsten-based composite material.
In the preparation process of the tungsten-wire-reinforced tungsten-based composite material, the present application first prepares a three-dimensional tungsten wire braid, which is prepared according to a method well known to those skilled in the art, and the present application is not particularly limited. In the application, the diameter of the tungsten wire in the three-dimensional tungsten wire woven body is 20-500 μm, and specifically, the diameter of the tungsten wire is 20-300 μm; the tungsten wire can be potassium-doped tungsten wire (W-K), tungsten-rhenium wire (W-Re) and rare earth oxide dispersion strengthened tungsten wire (W-La) 2 O 3 、W-Y 2 O 3 ) Etc. of. The three-dimensional tungsten filament woven body is doped with tungsten filaments which are long fibers, and the fiber reinforcement body is obtained after three-dimensional weaving, wherein the volume proportion of the tungsten filaments is 2-40%, and more specifically, the volume proportion of the tungsten filaments is 2-30%.
The three-dimensional tungsten filament braid is first subjected to chemical vapor deposition according to a method well known to those skilled in the art, and the present application is not particularly limited. In the chemical vapor deposition process, the volume ratio of raw materials is 1: 2-1, 4, and hydrogen, wherein the chemical vapor deposition temperature is 400-600 ℃, and the pressure is 10-100 kPa; specifically, the volume ratio of the tungsten hexafluoride to the hydrogen is 1. According to the method, the chemical vapor deposition is carried out firstly, because the porosity of the three-dimensional tungsten filament woven body is high, an auxiliary tool is required for forming, the tungsten filaments can be connected through the chemical vapor deposition, the strength of the woven body is improved, and the auxiliary tool can be removed in the subsequent steps.
The three-dimensional tungsten wire braided body compounded with the tungsten coating is soaked in tungsten powder slurry, and then drying and presintering are sequentially carried out, so that the three-dimensional tungsten wire braided body filled with the tungsten material is obtained. In the process, the tungsten powder slurry comprises tungsten powder and anhydrous ethanol, wherein the granularity of the tungsten powder is 0.5-5 mu m, the mass content of the tungsten powder is 60-95%, specifically, the granularity of the tungsten powder is 0.7-3 mu m, and the mass content of the tungsten powder is 75-95%. In the process, the three-dimensional tungsten wire braided body compounded with the tungsten coating is soaked in the tungsten powder slurry, under the conditions of ultrasound and heating, the anhydrous ethanol in the tungsten powder slurry is completely evaporated, and the tungsten powder is filled in the pores of the braided body, so that the porosity of the braided body is improved.
According to the invention, drying and pre-burning the three-dimensional tungsten wire braided body impregnated with the tungsten powder slurry to obtain the three-dimensional tungsten wire braided body impregnated with the tungsten powder slurry; in the process, the presintering atmosphere is hydrogen atmosphere, and the presintering temperature is 1200-1600 ℃; more specifically, the temperature of the pre-sintering is 1300-1500 ℃. The steps of slurry dipping, drying and presintering are circulated for more than 4 times, and the relative density of the three-dimensional tungsten filament braided body dipped by the tungsten powder slurry reaches more than 60 percent.
Dipping the three-dimensional tungsten wire braid impregnated by the tungsten powder slurry in tungstate impregnating solution, and then sequentially calcining, reducing and presintering to obtain a presintering body; in this process, the tungstate is metatungstate, and in a specific embodiment, the tungstate is ammonium metatungstate; the tungstate impregnating solution is a tungstate aqueous solution, and the mass concentration of the tungstate aqueous solution is 50-95%, more specifically 60-90%; in the process, the three-dimensional tungsten wire braided body impregnated with the tungsten powder slurry is soaked in tungstate impregnating solution, under the conditions of ultrasound and heating, water in the impregnating solution is completely evaporated, and tungstate is filled in gaps of the braided body, so that the porosity of the braided body is improved.
According to the invention, then calcining, reducing and presintering the three-dimensional tungsten wire braided body impregnated by the tungstate impregnating solution to obtain a presintered body; in the process, the calcination is carried out in an air atmosphere, the calcination temperature is 600-1000 ℃, and the tungstate is converted into tungsten oxide in the calcination process; the reducing atmosphere is hydrogen atmosphere, the reducing temperature is 700-900 ℃, and the tungsten oxide is reduced into tungsten in the reducing process; the presintering atmosphere is hydrogen atmosphere, and the presintering temperature is 1200-1600 ℃; more specifically, the calcining temperature is 700-900 ℃, the reducing temperature is 750-850 ℃, and the presintering temperature is 1300-1500 ℃. The processes of tungstate dipping, calcining, reducing and presintering are circulated for more than 4 times, and the relative density of the obtained presintered body reaches more than 70%.
According to the method, the tungsten materials are connected among the tungsten filaments of the braided body by adopting a chemical vapor deposition method, so that the strength of the braided body is improved, and an auxiliary tool in the initial three-dimensional tungsten filament braided body is removed; at the stage of low porosity of the woven body, a tungsten powder slurry dipping method is adopted, so that the filling efficiency is improved; and at the stage of higher porosity of the woven body, a tungstate impregnation method is adopted to ensure better filling effect. Therefore, the chemical vapor deposition method, the tungsten powder slurry impregnation method and the tungstate impregnation method are combined, the filling efficiency and the filling effect are improved, and the three-dimensional strength and the three-dimensional density of the woven body are improved.
The method comprises the steps of sequentially sintering and pressure processing a pre-sintered body to obtain a tungsten filament reinforced tungsten-based composite material; in the process, the sintering is carried out in a hydrogen atmosphere, the sintering temperature is 1600-2000 ℃, specifically, the sintering temperature is 1700-1900 ℃, and the relative density of the obtained tungsten filament reinforced tungsten-based composite material sintered body is more than 90%; the pressure processing mode is forging, the pressure processing temperature is 1200-1700 ℃, the deformation amount of the pressure processing is 20-95%, specifically, the pressure processing temperature is 1250-1650 ℃, and the deformation amount of the pressure processing is 30-85%.
The application provides a preparation method of a tungsten filament reinforced tungsten-based composite material, which comprises the steps of firstly adopting a chemical vapor deposition method to preliminarily fill a tungsten filament three-dimensional braiding body, and then sequentially adopting methods of tungsten powder slurry impregnation reduction pre-sintering and tungstate impregnation calcination reduction pre-sintering to fill the tungsten material into the tungsten filament three-dimensional braiding body, wherein the method has the following advantages: 1) The tungsten materials are connected among the tungsten filaments of the braided body by adopting a chemical vapor deposition method, so that the strength of the braided body is improved, and an auxiliary tool in the three-dimensional tungsten filament braided body is removed; 2) At the stage of low porosity of the woven body, a tungsten powder slurry dipping method is adopted, so that the filling efficiency is improved, and the cost is reduced; at the stage of higher porosity of the woven body, a tungstate impregnation method is adopted to ensure better filling effect; 3) In the step of tungstate impregnation, a method of tungstate reduction in-situ generation of tungsten powder is adopted, so that the tungsten powder filled in the tungsten filament three-dimensional woven body is uniform and compact, the granularity is controllable, and the densification of the three-dimensional tungsten filament woven body filled with tungsten materials after pre-sintering is realized. In conclusion, the chemical vapor deposition method, the tungsten powder slurry impregnation method and the tungstate impregnation method are combined, so that the filling efficiency and the filling effect are improved, and the three-dimensional strength, the three-dimensional toughness and the three-dimensional density of the woven body are improved through final solidification.
For further understanding of the present invention, the following detailed description is given to the technical field of tungsten filament reinforced tungsten-based composite materials provided by the present invention with reference to the following examples, and the scope of the present invention is not limited by the following examples.
Example one
In the embodiment, a potassium-doped tungsten filament is used as a raw material of the reinforcement, the potassium content of the tungsten filament is 50-70 ppm, the diameter of the tungsten filament is 50-60 μm, and the detailed preparation steps are as follows:
1) Preparing a tungsten filament three-dimensional woven body by adopting a stainless steel auxiliary tool, wherein the volume density of tungsten filaments in the woven body is about 9.7%;
2) Filling tungsten coatings in the pores of the tungsten filament three-dimensional braided body prepared in the step 1) by adopting a chemical vapor deposition method, wherein the tungsten filaments are prepared from WF (tungsten working fluid) 6 And H 2 In a ratio of 1:3, the deposition temperature is 540-550 ℃, the deposition pressure is 30kPa, the deposition time is 25min, the relative density of the three-dimensional tungsten wire braided body compounded with the tungsten coating obtained after deposition is about 18.5%, and the three-dimensional tungsten wire braided body compounded with the tungsten coating is machined to remove the stainless steel auxiliary tool;
3) Soaking the three-dimensional tungsten wire woven body compounded with the tungsten coating after the stainless steel auxiliary tool is removed in the step 2) into tungsten powder slurry, wherein the tungsten powder slurry for impregnation is a mixture of tungsten powder and absolute ethyl alcohol, the particle size of the tungsten powder is 0.8 mu m, the mass content of the tungsten powder in the slurry is 90%, under the heating conditions of ultrasound and 100 ℃, the absolute ethyl alcohol is completely evaporated to dryness, and the three-dimensional tungsten wire woven body filled with the tungsten material is obtained after presintering in 1370 ℃ hydrogen atmosphere; repeating the step for 4 times to obtain a three-dimensional tungsten filament braided body filled with tungsten materials, wherein the relative density of the three-dimensional tungsten filament braided body is about 66.9%;
4) Soaking the three-dimensional tungsten wire braid filled with the tungsten material obtained in the step 3) into an ammonium metatungstate water solution with the mass concentration of 75%, completely evaporating the water under ultrasonic and 100 ℃ heating conditions, and sequentially calcining in an air atmosphere at 600 ℃, reducing in a hydrogen atmosphere at 780 ℃ and presintering in a hydrogen atmosphere at 1360 ℃ to obtain a presintered body; this step was repeated 6 times to obtain a pre-sintered body having a relative density of about 73.9%;
5) Sintering the pre-sintered body obtained in the step 4) for 2 hours in a hydrogen atmosphere at 1780 ℃ to obtain a tungsten wire reinforced tungsten-based composite material sintered body, wherein the relative density of the sintered body is 93.5%; the tungsten wire reinforced tungsten-based composite material sintered body is forged in three dimensions at 1600 ℃, the deformation amounts in the three dimensions during independent forging are respectively 48%, 52% and 47%, and the density of the finally obtained tungsten wire reinforced tungsten-based composite material reaches 99.4%.
The prepared tungsten wire reinforced tungsten-based composite material is subjected to room temperature tensile property test in the three-dimensional direction, the ultimate tensile strength is 1452MPa, 1442MPa and 1473MPa respectively, the elongation after fracture is 7.4%, 8.5% and 7.8% respectively, and the average value is 1456MPa and 7.9% respectively; therefore, the ultimate tensile strength of the prepared tungsten filament reinforced tungsten-based composite material at room temperature is more than 1.4GPa, and the average elongation percentage after fracture at room temperature is more than 7 percent.
Example two
The procedure of this example is the same as that of example one, and a comparative example is also provided, and the procedure parameters and effects of each test example are detailed in table 1 (the procedure parameters not listed in table 1 are the same as that of example one) and table 2.
TABLE 1 parameter Table for each test example and comparative example of example II
| Silk material | Diameter of filament mum | Density of the knitted body | Particle size of tungsten powder | Tungstate reduction temperature DEG C | |
| Test example 2.1 | Potassium-doped tungsten wire | 70～90 | 9.4％ | 1.3 | 805 |
| Test example 2.2 | Potassium-doped tungsten wire | 50～60 | 6.5％ | 1.8 | 820 |
| Test example 2.3 | Potassium-doped tungsten wire | 150～170 | 7.1％ | 0.8 | 780 |
| Test example 2.4 | Lanthanum oxide doped tungsten wire | 90～110 | 10.4％ | 1.8 | 820 |
| Comparative example 2.5 | Potassium-doped tungsten wire | 70～90 | 9.4％ | 1.3 | 650 |
| Comparative example 2.6 | Potassium-doped tungsten wire | 70～90 | 9.4％ | 1.3 | 950 |
TABLE 2 Effect tables of the respective test examples and comparative examples of example II
Comparative example 1
The difference between the first comparative example and the first example is that the step 2) is omitted, and the other steps are the same as the first example, the relative density of the obtained tungsten wire reinforced tungsten-based composite sintered compact is 90.3%, the deformation amounts of the obtained tungsten wire reinforced tungsten-based composite sintered compact in the three-dimensional direction during single forging are 48%, 52% and 47%, and the density of the finally obtained tungsten wire reinforced tungsten-based composite is 96.2%.
The prepared tungsten wire reinforced tungsten-based composite material is subjected to room temperature tensile property test in the three-dimensional direction, the ultimate tensile strength is 776MPa, 796MPa and 803MPa, the elongation after fracture is 0.5%, 1.2% and 0.6%, and the average values are 792MPa and 0.8%, respectively, so that the average room temperature ultimate tensile strength of the prepared tungsten wire reinforced tungsten-based composite material is lower than 1.0GPa, and the average room temperature elongation after fracture is less than 3%.
Comparative example No. two
The difference between the second comparative example and the first example is that the step 3) is omitted, the other steps are the same as the first example, the relative density of the tungsten wire reinforced tungsten-based composite sintered compact obtained in the second comparative example is 86.8%, the deformation amounts of the obtained tungsten wire reinforced tungsten-based composite sintered compact in three-dimensional direction during single forging are 48%, 52% and 47%, and the density of the finally obtained tungsten wire reinforced tungsten-based composite is 95.3%.
The prepared tungsten wire reinforced tungsten-based composite material is subjected to room temperature tensile property test in the three-dimensional direction, the ultimate tensile strength obtained by the test is 685MPa, 609MPa and 701MPa, the elongation after fracture is 1.1%, 0.7% and 0.7%, and the average values are 665MPa and 0.8% respectively, so that the average room temperature ultimate tensile strength of the prepared tungsten wire reinforced tungsten-based composite material is lower than 1.0GPa, and the average room temperature elongation after fracture is less than 3%.
Comparative example No. three
The difference between the third comparative example and the first example is that the step 4) is omitted, the relative density of the obtained tungsten wire reinforced tungsten-based composite sintered body is 91.1%, the deformation amounts of the obtained tungsten wire reinforced tungsten-based composite sintered body during independent forging in the three-dimensional direction are 48%, 52% and 47%, and the density of the finally obtained tungsten wire reinforced tungsten-based composite is 97.2%.
The prepared tungsten wire reinforced tungsten-based composite material is subjected to room temperature tensile property test in the three-dimensional direction, the ultimate tensile strength is 862Pa, 893MPa and 834MPa through the test, the elongation after fracture is 1.2%, 0.7% and 1.3%, and the average values are 863MPa and 1.1% respectively, so that the average room temperature ultimate tensile strength of the prepared tungsten wire reinforced tungsten-based composite material is lower than 1.0GPa, and the average room temperature elongation after fracture is less than 3%.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A preparation method of a tungsten filament reinforced tungsten-based composite material comprises the following steps:
a) Carrying out chemical vapor deposition on the three-dimensional tungsten wire braided body to obtain a three-dimensional tungsten wire braided body compounded with a tungsten coating;
b) Dipping the three-dimensional tungsten wire braid compounded with the tungsten coating obtained in the step A) in tungsten powder slurry, and then sequentially drying and presintering to obtain a three-dimensional tungsten wire braid filled with tungsten materials; repeating for multiple times;
c) Dipping the three-dimensional tungsten wire braid filled with the tungsten material obtained in the step B) in tungstate dipping solution, then sequentially calcining, reducing and presintering to obtain a presintered body, and repeating the step for multiple times;
d) And C), sequentially sintering and pressure processing the pre-sintered body obtained in the step C) to obtain the tungsten filament reinforced tungsten-based composite material.
2. The method according to claim 1, wherein in step a), the diameter of the tungsten filament used in the three-dimensional tungsten filament woven body is 20 to 500 μm, and the purity of the tungsten filament is 99.99% or more;
preferably, the tungsten wire is further doped with one or more of potassium, rhenium and rare earth oxides.
3. The method according to claim 1, wherein in the step a), the volume ratio of the tungsten filament in the three-dimensional tungsten filament woven body is 2 to 40%.
4. The method according to claim 1, wherein in step a), the chemical vapor deposition is performed by using a raw material comprising 1: 2-1, 4, and hydrogen, wherein the temperature of the chemical vapor deposition is 400-600 ℃, and the pressure is 10-100 kPa.
5. The preparation method according to claim 1, wherein in the step B), the tungsten powder slurry comprises tungsten powder and absolute ethyl alcohol, the particle size of the tungsten powder is 0.5-5 μm, and the mass content of the tungsten powder is 60-95%.
6. The method according to claim 1, wherein in the step B), the atmosphere of the pre-firing is a hydrogen atmosphere, and the temperature of the pre-firing is 1200 to 1600 ℃.
7. The method according to claim 1, wherein the step B) is repeated 4 or more times, and the relative density of the three-dimensional tungsten filament braid filled with the tungsten material is 60% or more.
8. The preparation method according to claim 1, wherein in the step C), the tungstate is ammonium metatungstate, and the mass concentration of the tungstate impregnating solution is 50-95%.
9. The method according to claim 1, wherein in step C), the calcination is carried out in an air atmosphere, and the temperature of the calcination is 600 to 1000 ℃; the reducing atmosphere is hydrogen atmosphere, and the reducing temperature is 700-900 ℃; the presintering atmosphere is hydrogen atmosphere, and the presintering temperature is 1200-1600 ℃;
preferably, step C) is repeated 4 or more times, the relative density of the pre-sintered body being 70% or more.
10. The method according to claim 1, wherein in the step D), the sintering is performed in a hydrogen atmosphere, and the sintering temperature is 1600 to 2000 ℃;
preferably, in the step D), the pressure processing mode is forging, the forging temperature is 1200-1700 ℃, and the deformation is 20-95%;
preferably, in step D), the sintered body obtained by the sintering has a relative density of 90% or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211144036.8A CN115404419B (en) | 2022-09-20 | 2022-09-20 | Preparation method of tungsten wire reinforced tungsten-based composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211144036.8A CN115404419B (en) | 2022-09-20 | 2022-09-20 | Preparation method of tungsten wire reinforced tungsten-based composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115404419A true CN115404419A (en) | 2022-11-29 |
| CN115404419B CN115404419B (en) | 2023-09-01 |
Family
ID=84164876
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211144036.8A Active CN115404419B (en) | 2022-09-20 | 2022-09-20 | Preparation method of tungsten wire reinforced tungsten-based composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115404419B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102560292A (en) * | 2012-02-29 | 2012-07-11 | 中国科学院等离子体物理研究所 | Tungsten-based plasma facing material and preparation method thereof |
| JP5798279B1 (en) * | 2014-05-01 | 2015-10-21 | 昭和電工株式会社 | Method for manufacturing tungsten-based capacitor element |
| WO2015166670A1 (en) * | 2014-05-01 | 2015-11-05 | 昭和電工株式会社 | Method for manufacturing tungsten-based capacitor element |
| CN108251734A (en) * | 2016-12-28 | 2018-07-06 | 北京有色金属研究总院 | A kind of hot cathode tungsten basal body and preparation method thereof |
| CN112442643A (en) * | 2020-10-23 | 2021-03-05 | 合肥工业大学 | Layered fiber toughened tungsten-based composite material and preparation method thereof |
-
2022
- 2022-09-20 CN CN202211144036.8A patent/CN115404419B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102560292A (en) * | 2012-02-29 | 2012-07-11 | 中国科学院等离子体物理研究所 | Tungsten-based plasma facing material and preparation method thereof |
| JP5798279B1 (en) * | 2014-05-01 | 2015-10-21 | 昭和電工株式会社 | Method for manufacturing tungsten-based capacitor element |
| WO2015166670A1 (en) * | 2014-05-01 | 2015-11-05 | 昭和電工株式会社 | Method for manufacturing tungsten-based capacitor element |
| CN108251734A (en) * | 2016-12-28 | 2018-07-06 | 北京有色金属研究总院 | A kind of hot cathode tungsten basal body and preparation method thereof |
| CN112442643A (en) * | 2020-10-23 | 2021-03-05 | 合肥工业大学 | Layered fiber toughened tungsten-based composite material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 何培等: "面向等离子体钨基材料的增韧研究最新进展", 《功能材料》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115404419B (en) | 2023-09-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111644624B (en) | High-entropy alloy of refractory metal with porous structure and preparation method thereof | |
| CN108129167B (en) | High-temperature-resistant ablation-resistant modified ZrC-SiC ceramic coating and preparation method thereof | |
| CN107513674B (en) | A method of improving titanium aluminium layer shape microstructure of composite and improves mechanical property | |
| CN110079720B (en) | Gradient hard alloy and preparation method and application thereof | |
| CN114075078B (en) | High-temperature-resistant high-strength (Ti, zr, hf) C intermediate-entropy ceramic material and preparation method thereof | |
| CN114888292A (en) | Preparation method of high-strength superfine tungsten alloy wire for cutting | |
| CN111088450A (en) | Rare earth-added ultrafine-grained high-toughness WC-10Co hard alloy material and preparation method thereof | |
| CN115385712A (en) | High-entropy ultra-high temperature ceramic matrix composite and preparation method thereof | |
| CN114574789B (en) | Silicon carbide fiber, medium-high entropy ceramic reinforced metal matrix composite material and preparation method | |
| CN108588533A (en) | A kind of CVD coatings Ti (C, N) based ceramic metal basis material and preparation method thereof | |
| US9028584B2 (en) | System and method for fabrication of 3-D parts | |
| CN115404419B (en) | Preparation method of tungsten wire reinforced tungsten-based composite material | |
| AT501142B1 (en) | X-RAY TUBES WITH A ROSET AGENT COMPOSITE AND A METHOD FOR THE PRODUCTION THEREOF | |
| CN115124360B (en) | Carbon fiber toughened ceramic material and preparation method thereof | |
| CN114657433B (en) | Solid solution strengthening metal ceramic and preparation method thereof | |
| JP4051141B2 (en) | Tungsten, tungsten fiber reinforced composite material and molybdenum, molybdenum fiber reinforced composite material, manufacturing method thereof, and high-temperature component using the same | |
| CN115894082A (en) | (ZrHfTiTaNb) C-W metal high-entropy ceramic modified C/C composite material and preparation method thereof | |
| KR102314078B1 (en) | Manufacturing method for oxide dispersion strenthening alloys | |
| JP7380219B2 (en) | A surface-coated TiN-based cermet cutting tool with a hard coating layer that exhibits excellent chipping resistance. | |
| CN108083801B (en) | Three-dimensional carbon fiber prefabricated part reinforced yttrium oxide-zirconium oxide composite ceramic composite material and preparation method thereof | |
| CN106591747A (en) | Beta-Si3N4 whisker and Ni3Al binding phase synergistic toughened WC composite and preparation method thereof | |
| JPH0499146A (en) | Powder sintered material and its manufacture | |
| JP4542696B2 (en) | Rotating anode X-ray tube target and method for manufacturing the same | |
| JP4445141B2 (en) | Manufacturing method of inclined composite material | |
| CN114645172B (en) | Submicron gradient hard alloy with surface layer having cubic phase removed 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 |