CN112958770A - Preparation method of WRe/TZM composite material - Google Patents
Preparation method of WRe/TZM composite material Download PDFInfo
- Publication number
- CN112958770A CN112958770A CN202110141829.3A CN202110141829A CN112958770A CN 112958770 A CN112958770 A CN 112958770A CN 202110141829 A CN202110141829 A CN 202110141829A CN 112958770 A CN112958770 A CN 112958770A
- Authority
- CN
- China
- Prior art keywords
- wre
- tzm
- composite material
- alloy
- sintering
- 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.)
- Pending
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 81
- 239000000956 alloy Substances 0.000 claims abstract description 81
- 239000000843 powder Substances 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 47
- 238000002490 spark plasma sintering Methods 0.000 claims abstract description 19
- 239000006104 solid solution Substances 0.000 claims abstract description 16
- 238000005245 sintering Methods 0.000 claims description 41
- 238000010438 heat treatment Methods 0.000 claims description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 24
- 229910002804 graphite Inorganic materials 0.000 claims description 16
- 239000010439 graphite Substances 0.000 claims description 16
- 238000000498 ball milling Methods 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 12
- 238000000713 high-energy ball milling Methods 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 238000003825 pressing Methods 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000009792 diffusion process Methods 0.000 abstract description 6
- 230000017525 heat dissipation Effects 0.000 abstract description 4
- 230000035939 shock Effects 0.000 abstract description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 7
- 229910052721 tungsten Inorganic materials 0.000 description 7
- 239000010937 tungsten Substances 0.000 description 6
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 5
- 229910052702 rhenium Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- DECCZIUVGMLHKQ-UHFFFAOYSA-N rhenium tungsten Chemical compound [W].[Re] DECCZIUVGMLHKQ-UHFFFAOYSA-N 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 239000013077 target material Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 229910000691 Re alloy Inorganic materials 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 238000004663 powder metallurgy Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- CPTCUNLUKFTXKF-UHFFFAOYSA-N [Ti].[Zr].[Mo] Chemical compound [Ti].[Zr].[Mo] CPTCUNLUKFTXKF-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000013401 experimental design Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- WHJFNYXPKGDKBB-UHFFFAOYSA-N hafnium;methane Chemical compound C.[Hf] WHJFNYXPKGDKBB-UHFFFAOYSA-N 0.000 description 1
- 238000001513 hot isostatic pressing Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- NFFIWVVINABMKP-UHFFFAOYSA-N methylidynetantalum Chemical compound [Ta]#C NFFIWVVINABMKP-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910003468 tantalcarbide Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
- B22F7/02—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
- B22F1/142—Thermal or thermo-mechanical treatment
-
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J35/00—X-ray tubes
- H01J35/02—Details
- H01J35/04—Electrodes ; Mutual position thereof; Constructional adaptations therefor
- H01J35/08—Anodes; Anti cathodes
- H01J35/10—Rotary anodes; Arrangements for rotating anodes; Cooling rotary anodes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
-
- 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
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
Abstract
The present invention provides a method for preparing a WRe/TZM composite using spark plasma sintering, wherein the WRe alloy powder is formed into a solid solution prior to spark plasma sintering. The WRe/TZM composite material for the CT machine anode target, which is prepared by the preparation method, has the advantages of high density, high bonding strength and hardness, uniform interface diffusion, good heat dissipation performance, good thermal shock resistance and the like.
Description
Technical Field
The present invention relates to a method of preparing a WRe/TZM composite material, and more particularly, to a method of preparing a WRe/TZM composite material using spark plasma sintering. The WRe/TZM composite material has the advantages of high relative density, high bonding strength and hardness, uniform interface diffusion, good heat dissipation performance, good thermal shock resistance and the like.
Background
Tungsten-rhenium (WRe) alloys are alloys composed of the elements tungsten and rhenium. The metal tungsten has the advantages of high melting point, excellent high-temperature performance and the like, has high atomic number, and can excite strong X rays under the bombardment of high-energy electron beams. However, pure tungsten as a target has the following disadvantages: the notch sensitivity effect exists, and the cracks are easy to further expand and deepen, so that the target material is failed. Rhenium metal does not have a brittle transition temperature and rhenium metal has a recrystallization temperature higher than tungsten. Therefore, the rhenium in the tungsten-rhenium alloy can obviously reduce the plastic-brittle transition temperature of the tungsten, can improve the mechanical property of the tungsten in a high-temperature area and inhibit crack propagation, so the tungsten-rhenium alloy is a common target surface material of a CT machine rotating anode target.
The TZM (titanium zirconium molybdenum) alloy has high melting point, high strength, high elastic modulus, small linear expansion coefficient, lower vapor pressure, good electric and thermal conductivity, excellent corrosion resistance, good high-temperature mechanical property and the like, thereby being widely applied to a plurality of fields, such as rocket nozzles, jet pipe throat liners, gas distribution valve bodies in torpedo engines, gas pipelines, CT machine X-ray tube anode target substrates and the like. The WRe/TZM composite material has good joint performance when connected together due to the characteristic that W and Mo can form a W/Mo solid solution, thereby combining the advantages of the WRe alloy and the TZM alloy.
The scanning part of the CT apparatus mainly includes an X-ray tube, a detector and a gantry. An X-ray tube is one of the core devices of a CT machine, and in which an anode target rotating in the X-ray tube generates X-rays when subjected to high-energy electron beam bombardment, and is a wearing part that needs to be replaced periodically. Statistically, more than 50% of the X-ray tube damage is caused by the failure of the anode target, since more than about 99% of the energy is converted into heat energy during the operation of the X-ray tube, only 1% of the energy is converted into X-rays, and the local temperature of the anode can even reach 2600 ℃. Therefore, the target surface material of the X-ray tube is required to have the capability of generating high-quality X-rays, and must also have the characteristics of high temperature resistance, large thermal shock resistance and good heat dissipation performance. Therefore, the anode target material usually selects WRe alloy as a target surface material, TZM alloy and graphite as a substrate supporting material.
The preparation method of the rotary anode target material comprises a powder metallurgy method, a chemical vapor deposition method, a hot-pressing welding method and the like, wherein the powder metallurgy method is the simplest and most convenient, hot isostatic pressing or hot-pressing sintering is adopted to prepare the double-layer WRe/TZM composite material, but the melting points of the two materials are greatly different, so that the compactness can hardly meet the requirement. At present, most rotary anode targets are prepared by the processes of powder prepressing, high-temperature sintering (1800-2200 ℃), hot forging treatment, annealing and the like. The process is complicated and the cost is high.
CN109065425A discloses an anode target disk of a CT bulb tube and a preparation method thereof. Wherein, tungsten powder, hafnium carbide powder, tantalum carbide powder and rare earth oxide Y are used2O3The powder and the rhenium powder are used for preparing the target surface material of the target disc, and high-temperature sintering at 1950-1980 ℃ is required.
CN109590476A discloses a method for preparing a high-density WRe/TZM gradient composite material by a one-step method. In the method, a gradient mold needs to be arranged, and a temperature gradient needs to be arranged in the sintering process, so that the sintering process is complex, and the problem of high sintering temperature still exists.
Therefore, a simple and effective method for preparing a high-density WRe/TZM composite material suitable for a rotary anode target is needed to be developed.
Disclosure of Invention
Technical problem
To overcome the disadvantages of the manufacturing methods in the prior art, the present invention provides a method for preparing a high density WRe/TZM composite material using Spark Plasma Sintering (SPS) technology.
Technical scheme
The invention is found through a large number of experiments that: before SPS sintering, the WRe alloy powder is made into W-Re solid solution by adopting a high-energy ball milling mode, the powder is refined, the sintering activity of the powder is increased, so that the sintering temperature of the WRe alloy powder can be obviously reduced, and the obtained composite material has high compactness.
The present invention provides a method for preparing a WRe/TZM composite using Spark Plasma Sintering (SPS), wherein the WRe alloy powder is formed into a solid solution prior to spark plasma sintering.
Forming the WRe alloy powder into a solid solution prior to spark plasma sintering can significantly reduce the sintering temperature and increase the densification of the material.
Preferably, the method comprises the steps of:
step 1: performing high-energy ball milling on the WRe alloy powder to form a W-Re solid solution;
step 2: performing vacuum drying on the TZM alloy powder and the W-Re solid solution subjected to ball milling;
and step 3: taking a graphite mold provided with a lining, wherein the graphite mold comprises an upper pressing head, a lower pressing head and a graphite lining; firstly, a lower pressure head is arranged on a die, then TZM alloy powder is arranged in the die, after prepressing, ball-milled WRe alloy powder is arranged in the die, prepressing is carried out, the upper pressure head and the lower pressure head are pressed tightly, and meanwhile, the height of the upper pressure head and the height of the lower pressure head exceeding a cover die are consistent;
and 4, step 4: and (3) wrapping a layer of carbon felt outside the mold filled with the raw materials in the step (3), then placing the mold into an SPS furnace chamber, vacuumizing to be lower than 10Pa, and introducing direct-current pulse current for sintering to prepare the WRe/TZM composite material.
Preferably, the ball milling pot is made of hard alloy
The ball milling tank has a ball material ratio of 10-30: the ball milling time is 10 hours or more, preferably 10 to 40 hours.
Preferably, the W-Re solid solution has an average particle diameter of 1 to 2 μm, and the TZM alloy powder has a Fischer-Tropsch type particle size of 2 to 3 μm.
Preferably, the Re content in the WRe alloy is 5 wt.% to 15 wt.%.
Preferably, in the step 3, the inner diameter of the graphite mold provided with the bushing is 30-70 mm; the pre-pressing pressure is 5-20 MPa.
Preferably, in step 4, the sintering process adopts a gradient temperature rise mode, and the parameters are set as follows:
the heating rate is as follows: heating from room temperature to 1200 ℃ at a heating rate of 50-200 ℃/min, heating to the highest sintering temperature at a heating rate of 10-50 ℃/min, and keeping the temperature for 1-15 min; after the heat preservation is finished, reducing the axial pressure to 0kN, cooling to room temperature along with the furnace, and taking out to obtain the WRe/TZM composite material; the axial pressure in the sintering process is 20-50 MPa; the maximum sintering temperature is as follows: 1400-1600 ℃.
More preferably, the parameters of the sintering process are as follows:
the heating rate is as follows: heating from room temperature to 1200 ℃ at the heating rate of 100 ℃/min, heating to the highest sintering temperature at the heating rate of 30 ℃/min, and keeping the temperature for 5 min; after the heat preservation is finished, reducing the axial pressure to 0kN, cooling to room temperature along with the furnace, and taking out to obtain the WRe/TZM composite material; axial pressure in the sintering process is 30 MPa; the maximum sintering temperature is as follows: 1400-1600 ℃.
Preferably, in the WRe/TZM composite material, the relative density of the WRe alloy and the TZM alloy reaches more than 95.0 percent, and more preferably, the relative density reaches more than 97.0 percent; vickers hardness of 410HV0.5Above and 200HV0.5The above; and the shear strength of the composite material joint reaches more than 110 MPa.
Advantageous effects
The sintering process condition is obtained based on univariate scientific experimental design and a large number of experimental grops, and under the condition, the comprehensive performance of the product is optimal.
Compared with the prior art, the invention has the beneficial effects that:
1. the WRe/TZM composite material for the CT machine anode target, which is prepared by the preparation method, has the advantages of high density, high bonding strength and hardness, uniform interface diffusion, good heat dissipation performance and good thermal shock resistance.
2. The invention adopts SPS sintering technology, and has the characteristics of short sintering time, low sintering temperature, low energy consumption, simple process flow, stable quality and strong operability, thereby reducing the production period and cost.
The high-density WRe/TZM composite material obtained by the invention has uniform tissue components, the relative densities of the WRe alloy and the TZM alloy reach more than 95.0 percent, and the Vickers hardness reaches 410HV0.5Above and 200HV0.5The shear strength of the composite material joint reaches more than 110MPa, and the use requirement of the rotary anode target for the X-ray tube of the CT machine is met.
Drawings
FIG. 1 is an XRD spectrum of the WRe alloy powder (before ball milling) used in example 1;
FIG. 2 is an XRD spectrum of WRe after ball milling in example 1.
Detailed Description
The present invention is further illustrated by the following examples, and various changes or modifications may be made by those skilled in the art after reading the present disclosure, which equivalents also fall within the scope of the appended claims, but the embodiments of the present invention are not limited thereto.
The spark plasma sintering furnace used in the following examples was a LABOX-6020 spark plasma sintering system (SPS) manufactured by Sinter Land of Japan, and the current type thereof was a direct current pulse current with a pulse ratio of 40: 7; the inner diameter of the graphite mold is 30-70 mm.
WRe alloy powder used in the following examples is from Mo, Onconcus, Inc., wherein Re content is 5 wt.% and average particle size is 8-10 μm; the TZM alloy powder is from the molybdenum industry Co Ltd of gold heaping city, and the Fisher particle size is 2-3 μm.
The test method comprises the following steps:
1. relative density: archimedes drainage method
2. Vickers hardness: DHV-1000Z Vickers hardness tester
3: shear strength of the composite material joint: IBTC-5000 in-situ tension-compression mechanical test system
Example 1
This example produces a highly dense WRe/TZM composite for CT machine X-ray tubes as follows:
1. weighing WRe alloy powder, and carrying out high-energy ball milling on the WRe alloy powder (QM-QM type omnibearing planetary ball mill; ball-material ratio is 10: 1, and rotating speed is 300 rpm); after ball milling is carried out for 30 hours, a W-Re solid solution is completely formed, and WRe alloy powder with the average grain size of 1-2 mu m is used as a WRe powder alloy layer. Performing vacuum drying and sieving on the ball-milled WRe alloy powder and the raw material TZM alloy powder;
2. installing a lower pressure head on a die with the inner diameter phi of 70mm, then installing TZM alloy powder, prepressing by adopting a manual hydraulic press, keeping the pressure at 10MPa for 2min, then installing WRe alloy powder, prepressing by adopting the pressure of 10MPa in the same way, finally installing an upper pressure head, pressing the upper pressure head and the lower pressure head tightly, and simultaneously enabling the upper pressure head and the lower pressure head to exceed the height of the sleeve die to be consistent; a layer of graphite paper with the thickness of 0.2mm is added between the sample and the mold and between the sample and the pressure head for separation, so that the sample and the graphite are prevented from reacting, and demolding is facilitated;
3. wrapping a layer of carbon felt with the thickness of 5mm outside the mold filled with the raw materials, and then putting the carbon felt into an SPS furnace chamber for sintering to obtain a high-density WRe/TZM composite material;
4. the sintering process comprises the following steps: applying axial pressure of 30MPa, starting sintering when vacuumizing to 10Pa, and comprising the following specific processes:
the heating rate is as follows: heating from room temperature to 1200 ℃ at a heating rate of 100 ℃/min, heating to 1550 ℃ at a heating rate of 30 ℃/min, stopping heating, and keeping the temperature for 5 min; after the heat preservation is finished, reducing the axial pressure to 0kN, and cooling to room temperature along with the furnace;
as can be seen from comparison of fig. 2 with fig. 1, after high energy ball milling, the diffraction peak of Re completely disappeared, the intensity of the X-ray diffraction peak was reduced, the peak appeared to be significantly broadened, and no new phase was generated during this process, indicating that the WRe alloy powder had completely formed a solid solution.
Through determination, the WRe/TZM gradient composite material obtained in the embodiment has the WRe alloy layer compactness reaching 97.78% and the TZM alloy layer compactnessThe degree reaches 97.45 percent, the interface diffusion is uniform, and the Vickers hardness of the WRe alloy layer and the TZM alloy layer is 435.35HV0.5And 202.4HV0.5The room-temperature shear strength of the joint reaches 130.43MPa, and the use requirement of the anode target of the X-ray tube of the CT machine is met.
Example 2
This example produces a highly dense WRe/TZM composite for CT machine X-ray tubes as follows:
1. weighing WRe alloy powder, and carrying out high-energy ball milling (QM-QM ball mill; ball-material ratio 15: 1, rotating speed 300rpm) on the WRe alloy powder; after ball milling is carried out for 20 hours, a W-Re solid solution is completely formed, and WRe alloy powder with the average grain size of 1-2 mu m is used as a WRe powder alloy layer. Performing vacuum drying and sieving on the ball-milled WRe alloy powder and the raw material TZM alloy powder;
2. installing a lower pressure head on a die with the inner diameter phi of 50, then installing TZM alloy powder, prepressing by adopting a manual hydraulic press with the pressure of 10MPa, maintaining the pressure for 2min, then installing WRe alloy powder, prepressing by adopting the pressure of 10MPa in the same way, finally installing an upper pressure head, compacting the upper pressure head and the lower pressure head, and simultaneously enabling the upper pressure head and the lower pressure head to be consistent in height exceeding the die set; a layer of graphite paper with the thickness of 0.2mm is added between the sample and the mold and between the sample and the pressure head for separation, so that the sample and the graphite are prevented from reacting, and demolding is facilitated;
3. wrapping a layer of carbon felt with the thickness of 5mm outside the mold filled with the raw materials, and then putting the carbon felt into an SPS furnace chamber for sintering to obtain a high-density WRe/TZM composite material;
4. the sintering process comprises the following steps: applying axial pressure of 30MPa, starting sintering when vacuumizing to 10Pa, and comprising the following specific processes:
the heating rate is as follows: heating from room temperature to 1200 ℃ at a heating rate of 100 ℃/min, heating to a sintering temperature of 1500 ℃ at a heating rate of 30 ℃/min, stopping heating, and keeping the temperature for 5 min; after the heat preservation is finished, reducing the axial pressure to 0kN, and cooling to room temperature along with the furnace;
through determination, the density of the WRe alloy layer of the WRe/TZM gradient composite material obtained in the embodiment reaches 97.87%, the density of the TZM alloy layer reaches 97.35%, the interface diffusion is uniform, and the WRe alloy layer and the TZM alloy layer are Vickers hardDegree of 432.74HV0.5And 201.42HV0.5The room-temperature shear strength of the joint reaches 120.6MPa, and the use requirement of the anode target of the X-ray tube of the CT machine is met.
Example 3
This example produces a highly dense WRe/TZM composite for CT machine X-ray tubes as follows:
1. weighing WRe alloy powder, and carrying out high-energy ball milling (QM-QM ball mill; ball-material ratio is 20: 1, and rotating speed is 300rpm) on the WRe alloy powder; after ball milling is carried out for 10 hours, a W-Re solid solution is completely formed, and WRe alloy powder with the average grain size of 1-2 mu m is used as a WRe powder alloy layer. Performing vacuum drying and sieving on the ball-milled WRe alloy powder and the raw material TZM alloy powder;
2. installing a lower pressure head on a die with the inner diameter phi of 30mm, then installing TZM alloy powder, prepressing by adopting a manual hydraulic press with the pressure of 10MPa, maintaining the pressure for 2min, then installing WRe alloy powder, prepressing by adopting the pressure of 10MPa in the same way, finally installing an upper pressure head, pressing the upper pressure head and the lower pressure head tightly, and simultaneously enabling the upper pressure head and the lower pressure head to exceed the height of the die set to be consistent; a layer of graphite paper with the thickness of 0.2mm is added between the sample and the mold and between the sample and the pressure head for separation, so that the sample and the graphite are prevented from reacting, and demolding is facilitated;
3. wrapping a layer of carbon felt with the thickness of 5mm outside the mold filled with the raw materials, and then putting the carbon felt into an SPS furnace chamber for sintering to obtain a high-density WRe/TZM composite material;
4. the sintering process comprises the following steps: applying axial pressure of 30MPa, starting sintering when vacuumizing to 10Pa, and comprising the following specific processes:
the heating rate is as follows: heating from room temperature to 1200 ℃ at a heating rate of 100 ℃/min, heating to 1450 ℃ at a heating rate of 30 ℃/min, stopping heating, and keeping the temperature for 5 min; after the heat preservation is finished, reducing the axial pressure to 0kN, and cooling to room temperature along with the furnace;
through determination, the WRe/TZM gradient composite material obtained in the embodiment has the advantages that the density of the WRe alloy layer reaches 97.21%, the density of the TZM alloy layer reaches 97.14%, the interface diffusion is uniform, and the Vickers hardness of the WRe alloy layer and the Vickers hardness of the TZM alloy layer are 418.04HV0.5And 211.61HV0.5Room temperature of the jointThe shearing strength reaches 114.07MPa, and the use requirement of the anode target of the X-ray tube of the CT machine is met.
Comparative example 1
WRe/TZM composites were prepared in the same process as example 1, except that the WRe alloy powder was not subjected to high energy ball milling.
Wherein the density of the WRe alloy layer is 91.20%, the density of the TZM alloy layer is 97.25%, and the Vickers hardness of the WRe alloy layer and the Vickers hardness of the TZM alloy layer are 310.80HV0.5、195.15HV0.5The room-temperature shear strength of the joint is 103.01 MPa. The compactness, the Vickers hardness and the shear strength are all lower than those of WRe/TZM composite materials prepared by high-energy ball-milling WRe alloy powder.
Claims (10)
1. A method for preparing a WRe/TZM composite using spark plasma sintering, wherein,
the WRe alloy powder is allowed to form a solid solution prior to spark plasma sintering.
2. The method of claim 1, wherein,
the method comprises the following steps:
step 1: performing high-energy ball milling on the WRe alloy powder to form a W-Re solid solution;
step 2: performing vacuum drying on the TZM alloy powder and the W-Re solid solution subjected to ball milling;
and step 3: taking a graphite mold provided with a lining, wherein the graphite mold comprises an upper pressing head, a lower pressing head and a graphite lining; firstly, a lower pressure head is arranged in a die, then TZM alloy powder is filled in the die, after prepressing, ball-milled WRe alloy powder is filled in the die, prepressing is carried out, an upper pressure head and the lower pressure head are pressed tightly, and meanwhile, the height of the upper pressure head and the height of the lower pressure head exceeding a cover die are consistent;
and 4, step 4: and (3) wrapping a layer of carbon felt outside the mold filled with the raw materials in the step (3), then placing the mold into an SPS furnace chamber, vacuumizing the furnace chamber to below 10Pa, and then introducing direct-current pulse current to sinter the mold to prepare the WRe/TZM composite material.
3. The method of claim 1 or 2,
the ball milling tank for high-energy ball milling is a hard alloy ball milling tank, and the ball-material ratio is 10-30: the ball milling time is 10 hours or more, preferably 10 to 40 hours.
4. The method of any one of claims 1 to 3,
the average particle diameter of the W-Re solid solution is 1 to 2 μm, the Fischer-Tropsch particle size of the TZM alloy powder is 2 to 3 μm,
preferably, the Re content in the WRe alloy is 5 wt.% to 15 wt.%.
5. The method of any one of claims 1 to 4,
in the step 3, the inner diameter of the graphite mold provided with the bushing is 30-70 mm; the pre-pressing pressure is 5-20 MPa, and the pressure maintaining time is 1-10 min.
6. The method of any one of claims 1 to 5,
in step 4, the sintering process adopts a gradient temperature rise mode, and the parameters are set as follows:
the heating rate is as follows: heating from room temperature to 1200 ℃ at a heating rate of 50-200 ℃/min, heating to the highest sintering temperature at a heating rate of 10-50 ℃/min, and keeping the temperature for 1-15 min; after the heat preservation time is finished, reducing the axial pressure to 0kN, cooling to room temperature along with the furnace, and taking out to obtain the WRe/TZM composite material; the axial pressure in the sintering process is 20-50 MPa; the maximum sintering temperature is as follows: 1400-1600 ℃.
7. The method of any one of claims 1 to 6,
the parameters of the sintering process are as follows:
the heating rate is as follows: heating from room temperature to 1200 ℃ at a heating rate of 100 ℃/min, heating to the highest sintering temperature at a heating rate of 30 ℃/min, and keeping the temperature for 5-10 min; after the heat preservation time is finished, reducing the axial pressure to 0kN, cooling to room temperature along with the furnace, and taking out to obtain the WRe/TZM composite material; axial pressure in the sintering process is 30 MPa; the maximum sintering temperature is as follows: 1400-1600 ℃.
8. The method of any one of claims 1 to 6,
in the WRe/TZM composite material, the relative density of the WRe alloy and the TZM alloy reaches more than 95.0 percent, and more preferably, the relative density reaches more than 97.0 percent; vickers hardness of 410HV0.5Above and 200HV0.5The above; and the shear strength of the composite material joint reaches more than 110 MPa.
9. WRe/TZM composites prepared according to the methods described herein.
10. The WRe/TZM composite of claim 9,
the WRe/TZM composite material has the relative density that the relative density of the WRe alloy and the TZM alloy reach more than 95.0 percent, and more preferably, the relative density reaches more than 97.0 percent; vickers hardness of 410HV0.5Above and 200HV0.5The above; and the shear strength of the composite material joint reaches more than 110 MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110141829.3A CN112958770A (en) | 2021-02-02 | 2021-02-02 | Preparation method of WRe/TZM composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110141829.3A CN112958770A (en) | 2021-02-02 | 2021-02-02 | Preparation method of WRe/TZM composite material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112958770A true CN112958770A (en) | 2021-06-15 |
Family
ID=76273281
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110141829.3A Pending CN112958770A (en) | 2021-02-02 | 2021-02-02 | Preparation method of WRe/TZM composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112958770A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116174721A (en) * | 2023-02-28 | 2023-05-30 | 安庆瑞迈特科技有限公司 | Method for improving density and density uniformity of WRe/TZM alloy target disc |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0174393A1 (en) * | 1983-12-02 | 1986-03-19 | General Electric Company | Method for producing high density tungsten-rhenium alloys |
| CN101942592A (en) * | 2010-08-04 | 2011-01-12 | 湖南科技大学 | Method for preparing molybdenum copper alloy by activated sintering |
| CN102139371A (en) * | 2011-05-04 | 2011-08-03 | 佛山市钜仕泰粉末冶金有限公司 | Tungsten alloy target material and preparation method thereof |
| CN106001566A (en) * | 2016-06-29 | 2016-10-12 | 华南理工大学 | High-strength high-entropy alloy NbMoTaWV and preparation method thereof |
| CN108330371A (en) * | 2018-03-02 | 2018-07-27 | 北京科技大学 | The method that a kind of nanometer of phase separation sintering prepares tungsten material |
| CN108359872A (en) * | 2018-03-27 | 2018-08-03 | 江西澳科新材料科技有限公司 | A kind of tungsten alloy and preparation method thereof |
| CN109590476A (en) * | 2018-12-21 | 2019-04-09 | 合肥工业大学 | The method that one-step method prepares high-compactness WRe/TZM gradient composites |
| CN110076345A (en) * | 2019-06-18 | 2019-08-02 | 合肥工业大学 | An a kind of step SPS preparation method of high-compactness WRe/TZM gradient abnormity composite material |
| CN110181050A (en) * | 2019-06-04 | 2019-08-30 | 合肥工业大学 | A kind of SPS sintering connection method of WRe/TZM/ graphite |
| CN111996434A (en) * | 2020-08-21 | 2020-11-27 | 南方科技大学 | Block titanium molybdenum niobium alloy and preparation method thereof |
-
2021
- 2021-02-02 CN CN202110141829.3A patent/CN112958770A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0174393A1 (en) * | 1983-12-02 | 1986-03-19 | General Electric Company | Method for producing high density tungsten-rhenium alloys |
| CN101942592A (en) * | 2010-08-04 | 2011-01-12 | 湖南科技大学 | Method for preparing molybdenum copper alloy by activated sintering |
| CN102139371A (en) * | 2011-05-04 | 2011-08-03 | 佛山市钜仕泰粉末冶金有限公司 | Tungsten alloy target material and preparation method thereof |
| CN106001566A (en) * | 2016-06-29 | 2016-10-12 | 华南理工大学 | High-strength high-entropy alloy NbMoTaWV and preparation method thereof |
| CN108330371A (en) * | 2018-03-02 | 2018-07-27 | 北京科技大学 | The method that a kind of nanometer of phase separation sintering prepares tungsten material |
| CN108359872A (en) * | 2018-03-27 | 2018-08-03 | 江西澳科新材料科技有限公司 | A kind of tungsten alloy and preparation method thereof |
| CN109590476A (en) * | 2018-12-21 | 2019-04-09 | 合肥工业大学 | The method that one-step method prepares high-compactness WRe/TZM gradient composites |
| CN110181050A (en) * | 2019-06-04 | 2019-08-30 | 合肥工业大学 | A kind of SPS sintering connection method of WRe/TZM/ graphite |
| CN110076345A (en) * | 2019-06-18 | 2019-08-02 | 合肥工业大学 | An a kind of step SPS preparation method of high-compactness WRe/TZM gradient abnormity composite material |
| CN111996434A (en) * | 2020-08-21 | 2020-11-27 | 南方科技大学 | Block titanium molybdenum niobium alloy and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| F. H. (SAM) FROES等: "Formation of W-Re Solid Solution by Mechanical Alloying", 《MATERIALS AND MANUFACTURING PROCESSES》 * |
| 殷为宏等: "《难熔金属材料与工程应用》", 30 June 2012 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116174721A (en) * | 2023-02-28 | 2023-05-30 | 安庆瑞迈特科技有限公司 | Method for improving density and density uniformity of WRe/TZM alloy target disc |
| CN116174721B (en) * | 2023-02-28 | 2023-11-03 | 安庆瑞迈特科技有限公司 | Method for improving density and density uniformity of WRe/TZM alloy target disc |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109590476B (en) | Method for preparing high-density WRe/TZM gradient composite material by one-step method | |
| EP2193538B1 (en) | X-ray anode having improved heat dissipation | |
| CN106825885B (en) | A kind of connection method of TZM alloy and WRe alloy under electric field-assisted | |
| CN110076345B (en) | One-step SPS preparation method of high-density WRe/TZM gradient special-shaped composite material | |
| CN110181050B (en) | WRe/TZM/graphite SPS sintering connection method | |
| AT504405A2 (en) | X-RAY IMAGING SYSTEM, X-RAY DEVICE, X-RAY AGGREGATE AND METHOD OF MANUFACTURING THE SAME | |
| CN108907630B (en) | Manufacturing method of W/Mo/graphite composite anode target material for X-ray tube of CT machine | |
| US8280008B2 (en) | X-ray rotating anode plate, and method for the production thereof | |
| CN108262483B (en) | SPS sintering connection method for tungsten and molybdenum dissimilar refractory metal | |
| CN109065425B (en) | Anode target disk for CT bulb tube and preparation method thereof | |
| CN108796333A (en) | A kind of W-Mo-Re-HfC alloy materials and preparation method thereof | |
| CN102059449A (en) | Diffusion welding method of tungsten alloy and tantalum alloy at low temperature | |
| CN112958770A (en) | Preparation method of WRe/TZM composite material | |
| US6595821B2 (en) | Rotary anode for X-ray tube comprising an Mo-containing layer and a W-containing layer laminated to each other and method of producing the same | |
| NL2028306B1 (en) | Method for preparing binderless wc-y2o3 cemented carbide by pressure-assisted cold and hot sintering | |
| CN109778050A (en) | A kind of WVTaTiZr infusibility high-entropy alloy and preparation method thereof | |
| CN115679282A (en) | Preparation method of titanium-silicon target material | |
| CN113909480B (en) | Preparation method of in-situ nano zirconium oxide particle dispersion reinforced tungsten alloy | |
| CN110343932B (en) | WVTaZrSc refractory high-entropy alloy with high strength and preparation method thereof | |
| CN115747550B (en) | TiC particle reinforced high-strength high-wear-resistance tungsten-based composite material and preparation method thereof | |
| CN116475423A (en) | W/TZM composite material and preparation method thereof | |
| JP2002329470A (en) | Rotating anode for x-ray tube, and its manufacturing method | |
| CN115178852B (en) | Diffusion connection method for connecting tungsten and stainless steel | |
| CN115927898B (en) | TiC particle reinforced high-strength TZM-based composite material and preparation method thereof | |
| CN113881922B (en) | Method for preparing high-density W-Ti alloy sputtering target material at low temperature |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210615 |