CN113061766A - Method for improving high-temperature strength of tungsten-rhenium alloy - Google Patents
Method for improving high-temperature strength of tungsten-rhenium alloy Download PDFInfo
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- 229910000691 Re alloy Inorganic materials 0.000 title claims abstract description 141
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- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 229910052702 rhenium Inorganic materials 0.000 claims description 17
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- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
-
- 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
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
- C22C27/04—Alloys based on tungsten or molybdenum
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/0047—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents
- C22C32/0052—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents only carbides
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- 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
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
Abstract
The invention discloses a method for improving high-temperature strength of a tungsten-rhenium alloy, which comprises the following steps: firstly, accurately weighing W powder, Re powder and HfC powder according to the component content of each element in the tungsten-rhenium alloy, and carrying out high-energy ball milling in an inert atmosphere to obtain mixed alloy powder; and secondly, filling the mixed alloy powder into a graphite die for rapid discharge plasma sintering, and cooling along with the furnace to obtain the tungsten-rhenium alloy. The invention adopts the high-energy ball milling combined with the rapid discharge plasma sintering process at high temperature, effectively refines the crystal grains, improves the compactness of the tungsten-rhenium alloy, and enables the HfC to have a carbonization coarsening process, so that the HfC is distributed in the matrix crystal and at the crystal boundary and has various different sizes, a multi-size strengthening effect is generated, the high-temperature strength of the tungsten-rhenium alloy is effectively improved, the requirements on the application life of peripheral parts of a rocket nozzle, cone parts, engines or engine parts and the like are met, the preparation process flow is short, no environmental pollution is caused, and the economic benefit is high.
Description
Technical Field
The invention belongs to the technical field of powder metallurgy/composite materials, and particularly relates to a method for improving high-temperature strength of a tungsten-rhenium alloy.
Background
Tungsten (W) and its alloys have the advantages of high melting point (up to 3410 ℃), excellent high temperature strength, good thermal conductivity and corrosion resistance, and are widely used in rocket engine nozzles, turbines and combustors, nuclear reactors, kinetic energy puncturers, and the like. The tungsten-rhenium alloy (W-Re) combines the advantages of tungsten, and simultaneously refines the grain size of the tungsten by depending on the rhenium effect, thereby improving the mechanical property and the high-temperature stability of the tungsten.
The W-Re alloy has a series of excellent properties such as high melting point, high strength, high hardness, high plasticity, high recrystallization temperature, high resistivity, low vapor pressure, low electron work function, low plastic brittle transition temperature and the like due to the addition of rhenium. Therefore, the device has wide application in the aspects of electron, nuclear energy, spaceflight, temperature measurement and the like. Due to their high melting point and high temperature strength, W-Re alloys are also used as coatings for heat shields, rocket nozzle peripheral parts, cone parts, engines or engine parts of aerospace vehicles. With the research on W-Re alloy, the application potential of the W-Re alloy in the high-temperature field is further developed, the W-Re alloy is gradually expanded from the initial application of the W-Re alloy in thermocouple temperature measurement to the fields of nuclear energy, aerospace and the like, and the W-Re alloy has great application potential. As the use requirements of the high-temperature structural material are continuously improved, higher requirements are put on the performance of the W-Re alloy, and if the high-temperature structural material is required to have excellent high-temperature strength.
At present, the main problems of the mechanical properties of the W-Re alloy are mainly focused on that rhenium can cause the high-temperature mechanical properties of the alloy to be reduced, namely the melting point of the W-Re alloy is lower, for example, the melting point of W-26Re is about 400K lower than that of pure tungsten, and the reduction of the interatomic interaction force has little influence on the room-temperature mechanical properties, but has great influence on the high-temperature mechanical properties. It has been found in the prior art that the addition of rhenium to tungsten can increase the plasticity and room temperature strength of the tungsten material, but excessive rhenium conversely reduces the high temperature strength of the tungsten material, and rhenium is a rare noble metal, and the high rhenium content inevitably causes the cost increase. It is therefore necessary to find a suitable method for ensuring excellent high temperature mechanical properties of W-Re alloys while reducing the rhenium content.
In recent years, carbides/nitrides (TiC, HfC, ZrC, TiN, ZrN, etc.) have been used as reinforcements to improve mechanical properties of metal materials, and to enhance ablation resistance by dispersion strengthening at normal and high temperatures. However, at present, there is no systematic research on the preparation, processing, microstructure and mechanical properties of the carbide reinforced W-Re alloy, and the strengthening mechanism is not clarified, so that necessary guidance cannot be provided for reasonable application of the carbide reinforced W-Re alloy. Therefore, research on carbide reinforced W-Re alloy is necessary to obtain relevant reinforcing technology.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide a method for improving the high temperature strength of the tungsten-rhenium alloy in view of the above-mentioned deficiencies of the prior art. The method adopts a high-energy ball milling combined with a rapid discharge plasma sintering process at high temperature, effectively refines crystal grains, improves the compactness of the tungsten-rhenium alloy, and enables the HfC to have a carbonization coarsening process, so that the HfC is distributed in the matrix crystal and at the crystal boundary and has various different sizes, a multi-size strengthening effect is generated, and the high-temperature strength of the tungsten-rhenium alloy is effectively improved.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a method for improving the high-temperature strength of a tungsten-rhenium alloy is characterized by comprising the following steps:
firstly, accurately weighing W powder, Re powder and HfC powder according to the component contents of elements in the tungsten-rhenium alloy, and carrying out high-energy ball milling in an inert atmosphere to obtain mixed alloy powder;
step two, the mixed alloy powder obtained in the step one is put into a graphite die for rapid discharge plasma sintering, and the tungsten-rhenium alloy is obtained after furnace cooling; the rapid discharge plasma sintering process comprises the following steps: under the pressure condition of 30-60 MPa, the temperature is firstly increased to 1200 ℃ at the speed of 20 ℃/min, then is increased to 2400 ℃ at the speed of 5 ℃/min, and is kept for 25-35 min.
According to the invention, through high-energy ball milling, the crystal grains of each raw material powder in the mixed alloy powder are refined by adopting a mechanical alloying method, and the crystal grains are further refined by combining with the addition of HfC powder, so that the tungsten-rhenium alloy is strengthened, the density of the tungsten-rhenium alloy is improved, the hardness of the tungsten-rhenium alloy is increased, and the high-temperature strength and the toughness of the tungsten-rhenium alloy are greatly improved; meanwhile, a rapid discharge plasma sintering process is adopted, impurity oxygen in raw materials is effectively removed by rapidly heating to 1200 ℃, the formation of a softening phase is avoided, then slowly heating to 2400 ℃ and preserving heat are carried out, so that the HfC is subjected to a carbonization coarsening process, namely, selective particle growth is carried out at the crystal boundary and dislocation line of a tungsten-rhenium alloy matrix, and partial nano HfC particles exist in the crystal, namely at partial crystal boundary, so that the HfC is distributed in the matrix crystal and at the crystal boundary and has various different sizes, a multi-size strengthening effect is generated, and the high-temperature strength of the tungsten-rhenium alloy is effectively improved.
The method for improving the high-temperature strength of the tungsten-rhenium alloy is characterized in that in the step one, the mass purity of the W powder is 99.9 percent, the average grain diameter is 5 microns, the mass purity of the Re powder is 99.95 percent, the average grain diameter is 2 microns, the mass purity of the HfC powder is 99.9 percent, and the average grain diameter is 1 micron.
The method for improving the high-temperature strength of the tungsten-rhenium alloy is characterized in that in the step one, the high-energy ball milling is carried out by adopting a QM-3SP2 planetary ball mill, the adopted ball milling pot is an agate pot, the grinding balls are agate balls, the rotation speed of the high-energy ball milling is 350-450 rpm, the time is 35-45 h, and the ball-to-material ratio is 10-15: 1. by controlling the technological parameters and conditions of the high-energy ball milling, the grains of the raw material powder are fully refined, and meanwhile, the oxidation agglomeration of the raw material powder is avoided.
The method for improving the high-temperature strength of the tungsten-rhenium alloy is characterized in that absolute ethyl alcohol is added as a control agent in the high-energy ball milling process in the step one, and the addition amount of the control agent is 10-20% of the total mass of the W powder, the Re powder and the HfC powder.
The method for improving the high-temperature strength of the tungsten-rhenium alloy is characterized in that in the step one, after the high-energy ball milling is finished, the mixed alloy powder is cleaned for 2-3 times by using absolute ethyl alcohol, the mass of the absolute ethyl alcohol used for cleaning is 5-10 times of the total mass of the W powder, the Re powder and the HfC powder, the cleaned mixed alloy powder is subjected to vacuum drying, the temperature of the vacuum drying is 40-60 ℃, and the drying time is 3-5 hours.
The method for improving the high-temperature strength of the tungsten-rhenium alloy is characterized in that in the second step, graphite paper is laid on the inner surface of a graphite mold, then mixed alloy powder is filled in the graphite paper, and the graphite mold is fixed outside by a carbon fiber mold. Through the arrangement, the phenomenon that the mixed alloy powder cracks in a mould due to the fact that the thermal expansion coefficient is too large in the sintering process, damage to equipment is caused, and smooth proceeding of the subsequent sintering process is guaranteed.
The method for improving the high-temperature strength of the tungsten-rhenium alloy is characterized in that argon is introduced for protection in the rapid discharge plasma sintering process in the step two, and the tungsten-rhenium alloy is taken out of the furnace after being cooled to room temperature along with the furnace. Air is prevented from entering the furnace through argon protection, and the sintering quality is guaranteed.
The method for improving the high-temperature strength of the tungsten-rhenium alloy is characterized in that in the second step, the composition of the tungsten-rhenium alloy is W-3Re-xHfC, wherein the mass content of W is 97%, the mass content of Re is 3%, the mass of HfC is x% of the total mass of W and Re, and x is more than 0 and less than or equal to 10. According to the invention, the HfC is introduced, so that the Re mass content in the tungsten-rhenium alloy is reduced to 3%, the Re raw material cost is reduced, and the high-temperature strength of the tungsten-rhenium alloy is improved.
Compared with the prior art, the invention has the following advantages:
1. according to the invention, through high-energy ball milling, the crystal grains of each raw material powder in the mixed alloy powder are refined by adopting a mechanical alloying method, the crystal grains are further refined by combining with the addition of HfC powder, the strengthening of the tungsten-rhenium alloy is realized, the high-temperature strength and toughness of the tungsten-rhenium alloy are improved, and meanwhile, the density of the tungsten-rhenium alloy is further improved and the hardness of the tungsten-rhenium alloy is increased by adopting a rapid discharge plasma sintering process at high temperature, so that the high-temperature strength of the tungsten-rhenium alloy is greatly improved.
2. According to the invention, the unique coarsening effect of HfC is fully utilized, the HfC is coarsened by controlling the temperature of rapid discharge plasma sintering, namely selective particle growth is carried out at the crystal boundary and dislocation line of the tungsten-rhenium alloy matrix, and partial nano HfC particles exist in the crystal, namely part of the crystal boundary, so that HfC is distributed in the matrix crystal and at the crystal boundary and has various different sizes, a multi-size strengthening effect is generated, and the high-temperature strength of the tungsten-rhenium alloy is effectively improved.
3. According to the invention, through research on tungsten-rhenium alloys with different HfC mass contents, the mechanism for improving the high-temperature strength of the tungsten-rhenium alloy comprises a crystal grain strengthening phase, an Orowan strengthening phase and an interface thermal mismatch strengthening phase, and along with the increase of the HfC mass content in a certain range, the hardness of the tungsten-rhenium alloy is higher, and the high-temperature strength is higher, namely the HfC mass content in the tungsten-rhenium alloy is in direct proportion to the total high-temperature strength.
4. Compared with the traditional high-temperature alloy, rare earth doped tungsten alloy, tungsten-rhenium alloy, iridium/rhenium composite material and the like, the tungsten-rhenium alloy prepared by the invention has better plasticity, keeps higher strength and hardness, and can meet the requirements of the application life of rocket nozzle peripheral components, cone components, engines or engine components and the like.
5. The preparation process of the invention has short flow, no environmental pollution and high economic benefit.
The technical solution of the present invention is further described in detail by the accompanying drawings and examples.
Drawings
FIG. 1a is a micro-topography of W powder in examples 1 to 6 of the present invention and comparative example 1.
FIG. 1b is a micro-topography of Re powder in examples 1 to 6 of the present invention and comparative example 1.
Fig. 1c is a micro-topography of the HfC powders of examples 1-6 of the present invention and comparative example 1.
Fig. 2a is a microstructure morphology of the tungsten-rhenium alloy prepared in comparative example 1 of the present invention.
Fig. 2b is a microstructure morphology of the tungsten-rhenium alloy prepared in example 3 of the present invention.
Fig. 2c is a microstructure morphology of the tungsten-rhenium alloy prepared in the embodiment 4 of the present invention.
Fig. 2d is a microstructure and topography of the tungsten-rhenium alloy prepared in example 5 of the present invention.
Fig. 2e is a microstructure morphology of the tungsten-rhenium alloy prepared in example 6 of the present invention.
Detailed Description
Example 1
The embodiment comprises the following steps:
firstly, accurately weighing W powder, Re powder and HfC powder respectively according to the component content of each element in the tungsten-rhenium alloy, placing the W powder, the Re powder and the HfC powder in a QM-3SP2 planetary ball mill for high-energy ball milling in an inert atmosphere, wherein the ball milling tank is an agate tank, the milling balls are agate balls, the rotation speed of the high-energy ball milling is 350rpm, the time is 35 hours, and the ball-to-material ratio is 10:1, so as to obtain mixed alloy powder;
the mass purity of the W powder is 99.9%, the average particle size is 5 microns, the mass purity of the Re powder is 99.95%, the average particle size is 2 microns, the mass purity of the HfC powder is 99.9%, and the average particle size is 1 micron; absolute ethyl alcohol is added as a control agent in the high-energy ball milling process, and the addition amount of the control agent is 10% of the total mass of the W powder, the Re powder and the HfC powder; after the high-energy ball milling is finished, cleaning the mixed alloy powder for 2 times by using absolute ethyl alcohol, wherein the mass of the absolute ethyl alcohol used for cleaning is 5 times of the total mass of the W powder, the Re powder and the HfC powder, and carrying out vacuum drying on the cleaned mixed alloy powder at the temperature of 40 ℃ for 3 hours;
secondly, laying graphite paper on the inner surface of a graphite mold, then filling the mixed alloy powder obtained in the first step into the graphite mold, fixing the graphite mold by adopting a carbon fiber mold, then carrying out rapid discharge plasma sintering, heating to 1200 ℃ at a speed of 20 ℃/min under the pressure condition of argon atmosphere and 30MPa, then heating to 2400 ℃ at a speed of 5 ℃/min, preserving heat for 25min, cooling to room temperature along with a furnace, and discharging to obtain the tungsten-rhenium alloy; the tungsten-rhenium alloy is composed of W-3Re-0.5HfC, wherein the mass content of W is 97%, the mass content of Re is 3%, and the mass of HfC is 0.5% of the total mass of W and Re.
Example 2
The embodiment comprises the following steps:
firstly, accurately weighing W powder, Re powder and HfC powder respectively according to the component content of each element in the tungsten-rhenium alloy, placing the W powder, the Re powder and the HfC powder in a QM-3SP2 planetary ball mill for high-energy ball milling in an inert atmosphere, wherein the adopted ball milling pot is an agate pot, grinding balls are agate balls, the rotation speed of the high-energy ball milling is 450rpm, the time is 45 hours, and the ball-to-material ratio is 15:1, so as to obtain mixed alloy powder;
the mass purity of the W powder is 99.9%, the average particle size is 5 microns, the mass purity of the Re powder is 99.95%, the average particle size is 2 microns, the mass purity of the HfC powder is 99.9%, and the average particle size is 1 micron; absolute ethyl alcohol is added as a control agent in the high-energy ball milling process, and the addition amount of the control agent is 20% of the total mass of the W powder, the Re powder and the HfC powder; cleaning the mixed alloy powder for 3 times by using absolute ethyl alcohol after the high-energy ball milling is finished, wherein the mass of the absolute ethyl alcohol used for cleaning is 10 times of the total mass of the W powder, the Re powder and the HfC powder, and carrying out vacuum drying on the cleaned mixed alloy powder at the temperature of 60 ℃ for 5 hours;
secondly, laying graphite paper on the inner surface of a graphite mold, then filling the mixed alloy powder obtained in the first step into the graphite mold, fixing the graphite mold by adopting a carbon fiber mold, then carrying out rapid discharge plasma sintering, heating to 1200 ℃ at a speed of 20 ℃/min under the pressure condition of argon atmosphere and 60MPa, then heating to 2100 ℃ at a speed of 5 ℃/min, preserving heat for 35min, cooling to room temperature along with a furnace, and discharging to obtain the tungsten-rhenium alloy; the tungsten-rhenium alloy is composed of W-3Re-10HfC, wherein the mass content of W is 97%, the mass content of Re is 3%, and the mass of HfC is 10% of the total mass of W and Re.
Example 3
The embodiment comprises the following steps:
firstly, accurately weighing W powder, Re powder and HfC powder respectively according to the component content of each element in the tungsten-rhenium alloy, placing the W powder, the Re powder and the HfC powder in a QM-3SP2 planetary ball mill for high-energy ball milling in an inert atmosphere, wherein the ball milling tank is an agate tank, the milling balls are agate balls, the rotation speed of the high-energy ball milling is 400rpm, the time is 40 hours, and the ball-to-material ratio is 12:1, so as to obtain mixed alloy powder;
the mass purity of the W powder is 99.9%, the average particle size is 5 microns, the mass purity of the Re powder is 99.95%, the average particle size is 2 microns, the mass purity of the HfC powder is 99.9%, and the average particle size is 1 micron; absolute ethyl alcohol is added as a control agent in the high-energy ball milling process, and the addition amount of the control agent is 15% of the total mass of the W powder, the Re powder and the HfC powder; cleaning the mixed alloy powder for 3 times by using absolute ethyl alcohol after the high-energy ball milling is finished, wherein the mass of the absolute ethyl alcohol used for cleaning is 8 times of the total mass of the W powder, the Re powder and the HfC powder, and carrying out vacuum drying on the cleaned mixed alloy powder at the temperature of 50 ℃ for 4 hours;
secondly, laying graphite paper on the inner surface of a graphite mold, then filling the mixed alloy powder obtained in the first step into the graphite mold, fixing the graphite mold by adopting a carbon fiber mold, then carrying out rapid discharge plasma sintering, heating to 1200 ℃ at a speed of 20 ℃/min under the pressure condition of 40MPa in an argon atmosphere, then heating to 2100 ℃ at a speed of 5 ℃/min, preserving heat for 30min, cooling to room temperature along with a furnace, and discharging to obtain the tungsten-rhenium alloy; the tungsten-rhenium alloy is composed of W-3Re-0.5HfC, wherein the mass content of W is 97%, the mass content of Re is 3%, and the mass of HfC is 0.5% of the total mass of W and Re.
Example 4
The embodiment comprises the following steps:
firstly, accurately weighing W powder, Re powder and HfC powder respectively according to the component content of each element in the tungsten-rhenium alloy, placing the W powder, the Re powder and the HfC powder in a QM-3SP2 planetary ball mill for high-energy ball milling in an inert atmosphere, wherein the ball milling tank is an agate tank, the milling balls are agate balls, the rotation speed of the high-energy ball milling is 400rpm, the time is 40 hours, and the ball-to-material ratio is 12:1, so as to obtain mixed alloy powder;
the mass purity of the W powder is 99.9%, the average particle size is 5 microns, the mass purity of the Re powder is 99.95%, the average particle size is 2 microns, the mass purity of the HfC powder is 99.9%, and the average particle size is 1 micron; absolute ethyl alcohol is added as a control agent in the high-energy ball milling process, and the addition amount of the control agent is 15% of the total mass of the W powder, the Re powder and the HfC powder; cleaning the mixed alloy powder for 3 times by using absolute ethyl alcohol after the high-energy ball milling is finished, wherein the mass of the absolute ethyl alcohol used for cleaning is 8 times of the total mass of the W powder, the Re powder and the HfC powder, and carrying out vacuum drying on the cleaned mixed alloy powder at the temperature of 50 ℃ for 4 hours;
secondly, laying graphite paper on the inner surface of a graphite mold, then filling the mixed alloy powder obtained in the first step into the graphite mold, fixing the graphite mold by adopting a carbon fiber mold, then carrying out rapid discharge plasma sintering, heating to 1200 ℃ at a speed of 20 ℃/min under the pressure condition of 40MPa in an argon atmosphere, then heating to 2100 ℃ at a speed of 5 ℃/min, preserving heat for 30min, cooling to room temperature along with a furnace, and discharging to obtain the tungsten-rhenium alloy; the tungsten-rhenium alloy is composed of W-3Re-1HfC, wherein the mass content of W is 97%, the mass content of Re is 3%, and the mass of HfC is 1% of the total mass of W and Re.
Example 5
The embodiment comprises the following steps:
firstly, accurately weighing W powder, Re powder and HfC powder respectively according to the component content of each element in the tungsten-rhenium alloy, placing the W powder, the Re powder and the HfC powder in a QM-3SP2 planetary ball mill for high-energy ball milling in an inert atmosphere, wherein the ball milling tank is an agate tank, the milling balls are agate balls, the rotation speed of the high-energy ball milling is 400rpm, the time is 40 hours, and the ball-to-material ratio is 12:1, so as to obtain mixed alloy powder;
the mass purity of the W powder is 99.9%, the average particle size is 5 microns, the mass purity of the Re powder is 99.95%, the average particle size is 2 microns, the mass purity of the HfC powder is 99.9%, and the average particle size is 1 micron; absolute ethyl alcohol is added as a control agent in the high-energy ball milling process, and the addition amount of the control agent is 15% of the total mass of the W powder, the Re powder and the HfC powder; cleaning the mixed alloy powder for 3 times by using absolute ethyl alcohol after the high-energy ball milling is finished, wherein the mass of the absolute ethyl alcohol used for cleaning is 8 times of the total mass of the W powder, the Re powder and the HfC powder, and carrying out vacuum drying on the cleaned mixed alloy powder at the temperature of 50 ℃ for 4 hours;
secondly, laying graphite paper on the inner surface of a graphite mold, then filling the mixed alloy powder obtained in the first step into the graphite mold, fixing the graphite mold by adopting a carbon fiber mold, then carrying out rapid discharge plasma sintering, heating to 1200 ℃ at a speed of 20 ℃/min under the pressure condition of 40MPa in an argon atmosphere, then heating to 2100 ℃ at a speed of 5 ℃/min, preserving heat for 30min, cooling to room temperature along with a furnace, and discharging to obtain the tungsten-rhenium alloy; the tungsten-rhenium alloy is composed of W-3Re-5HfC, wherein the mass content of W is 97%, the mass content of Re is 3%, and the mass of HfC is 5% of the total mass of W and Re.
Example 6
The embodiment comprises the following steps:
firstly, accurately weighing W powder, Re powder and HfC powder respectively according to the component content of each element in the tungsten-rhenium alloy, placing the W powder, the Re powder and the HfC powder in a QM-3SP2 planetary ball mill for high-energy ball milling in an inert atmosphere, wherein the ball milling tank is an agate tank, the milling balls are agate balls, the rotation speed of the high-energy ball milling is 400rpm, the time is 40 hours, and the ball-to-material ratio is 12:1, so as to obtain mixed alloy powder;
the mass purity of the W powder is 99.9%, the average particle size is 5 microns, the mass purity of the Re powder is 99.95%, the average particle size is 2 microns, the mass purity of the HfC powder is 99.9%, and the average particle size is 1 micron; absolute ethyl alcohol is added as a control agent in the high-energy ball milling process, and the addition amount of the control agent is 15% of the total mass of the W powder, the Re powder and the HfC powder; cleaning the mixed alloy powder for 3 times by using absolute ethyl alcohol after the high-energy ball milling is finished, wherein the mass of the absolute ethyl alcohol used for cleaning is 8 times of the total mass of the W powder, the Re powder and the HfC powder, and carrying out vacuum drying on the cleaned mixed alloy powder at the temperature of 50 ℃ for 4 hours;
secondly, laying graphite paper on the inner surface of a graphite mold, then filling the mixed alloy powder obtained in the first step into the graphite mold, fixing the graphite mold by adopting a carbon fiber mold, then carrying out rapid discharge plasma sintering, heating to 1200 ℃ at a speed of 20 ℃/min under the pressure condition of 40MPa in an argon atmosphere, then heating to 2100 ℃ at a speed of 5 ℃/min, preserving heat for 30min, cooling to room temperature along with a furnace, and discharging to obtain the tungsten-rhenium alloy; the tungsten-rhenium alloy is composed of W-3Re-10HfC, wherein the mass content of W is 97%, the mass content of Re is 3%, and the mass of HfC is 10% of the total mass of W and Re.
Comparative example 1
This comparative example comprises the following steps:
firstly, accurately weighing W powder and Re powder respectively according to the component content of each element in the tungsten-rhenium alloy, placing the W powder and the Re powder in a QM-3SP2 planetary ball mill for high-energy ball milling in an inert atmosphere, wherein the adopted ball milling pot is an agate pot, the milling balls are agate balls, the rotation speed of the high-energy ball milling is 400rpm, the time is 40 hours, and the ball-to-material ratio is 12:1, so as to obtain mixed alloy powder;
the mass purity of the W powder is 99.9%, the average particle size is 5 μm, the mass purity of the Re powder is 99.95%, and the average particle size is 2 μm; absolute ethyl alcohol is added as a control agent in the high-energy ball milling process, and the addition amount of the control agent is 15% of the total mass of the W powder and the Re powder; cleaning the mixed alloy powder for 3 times by using absolute ethyl alcohol after the high-energy ball milling is finished, wherein the mass of the absolute ethyl alcohol used for cleaning is 8 times of the total mass of the W powder and the Re powder, and carrying out vacuum drying on the cleaned mixed alloy powder at the temperature of 50 ℃ for 4 hours;
secondly, laying graphite paper on the inner surface of a graphite mold, then filling the mixed alloy powder obtained in the first step into the graphite mold, fixing the graphite mold by adopting a carbon fiber mold, then carrying out rapid discharge plasma sintering, heating to 1200 ℃ at a speed of 20 ℃/min under the pressure condition of 40MPa in an argon atmosphere, then heating to 2100 ℃ at a speed of 5 ℃/min, preserving heat for 30min, cooling to room temperature along with a furnace, and discharging to obtain the tungsten-rhenium alloy; the tungsten-rhenium alloy has the composition of W-3Re, wherein the mass content of W is 97%, and the mass content of Re is 3%.
The actually measured density, the theoretical density, the relative density and the microhardness of the tungsten-rhenium alloy prepared in the embodiments 3 to 6 and the comparative example 1 are respectively detected, and the results are shown in the following table 1.
TABLE 1
As can be seen from table 1, as the mass content (0% to 5%) of HfC in the tungsten-rhenium alloy increases, the relative density of the tungsten-rhenium alloy also increases, which indicates that the existence of a certain mass content of HfC particles is favorable for increasing the relative density of the tungsten-rhenium alloy, when the mass content of hf carbide exceeds 5%, the relative density of the tungsten-rhenium alloy decreases as the mass content of hf carbide increases (5% to 10%), when the mass content of HfC in the tungsten-rhenium alloy reaches about 10%, the uniform dispersion of the HfC particles in the W matrix becomes difficult, the aggregation of the HfC particles at the W grain boundary occurs, and part of the HfC particles cannot contact with the W particles, resulting in the decrease of the relative density of the tungsten-rhenium alloy. Thus, from a variation process analysis of the effect of an increase in the hafnium carbide mass content on the relative density of the tungsten-rhenium alloy, it follows: small amounts of HfC particles effectively activate the grain boundaries, promoting grain boundary sliding, GBs migration, but as the HfC content increases, the HfC particles agglomerate. Meanwhile, as the mass content of the hafnium carbide is increased (0-10%), the Vickers microhardness of the tungsten-rhenium alloy is also obviously increased, and particularly when the mass content of the hafnium carbide is 10% (example 6), the Vickers microhardness of the tungsten-rhenium alloy is about 659.4HV, which is 92.5% higher than that of the tungsten-rhenium alloy matrix (comparative example 1).
Fig. 1a is a micro-topography of W powder in examples 1 to 6 of the present invention and comparative example 1, fig. 1b is a micro-topography of Re powder in examples 1 to 6 of the present invention and comparative example 1, and fig. 1c is a micro-topography of HfC powder in examples 1 to 6 of the present invention and comparative example 1, and it can be seen from fig. 1a to 1c that the powder particle size of W powder is large, the powder is mainly composed of the size and the particle size, the powder of the larger particles is mainly in the form of a sphere, the powder of Re powder is dendritic, the particle size distribution of HfC powder is uniform, the average particle size is about 1 μm, some fine particles are aggregated, and the powder is mainly in the form of a polygon.
The structures of the tungsten-rhenium alloys prepared in examples 3 to 6 of the present invention and comparative example 1 were observed and examined, and the results are shown in fig. 2a to 2 e.
Fig. 2a is a microstructure and topography diagram of a tungsten-rhenium alloy prepared in comparative example 1 of the present invention, fig. 2b is a microstructure and topography diagram of a tungsten-rhenium alloy prepared in example 3 of the present invention, fig. 2c is a microstructure and topography diagram of a tungsten-rhenium alloy prepared in example 4 of the present invention, fig. 2d is a microstructure and topography diagram of a tungsten-rhenium alloy prepared in example 5 of the present invention, and fig. 2e is a microstructure and topography diagram of a tungsten-rhenium alloy prepared in example 6 of the present invention. As can be seen from FIG. 2a, the solid solution alloy matrix structure of the W-Re alloy without added HfC particles in the comparative example 1 is a typical dendritic structure, the average grain diameter is 8.8 μm, the structure is almost completely compact, and no obvious residual pores exist, while the W-Re alloy structures with added HfC particles in FIGS. 2 b-2 e contain W-Re matrix with light gray phase and HfC particles with deep gray phase, and the average grain diameter of the W-Re alloy with added HfC particles is obviously smaller than that of the W-Re alloy without added HfC particles in FIG. 2a, which shows that the HfC particles inhibit the grain growth of the W-Re alloy during high-temperature sintering, and play a role in grain refinement; meanwhile, as can be seen from fig. 2b to fig. 2e, due to the poor sinterability between the HfC particles and the poor compatibility between the HfC and the tungsten-rhenium matrix interface, a small amount of micropores exist in part of the HfC particle clusters, which may be a potential source for the formation of microcracks.
Obtaining a strengthening mechanism of the tungsten-rhenium alloy according to the observation and detection results: (1) grain refinement and reinforcement; (2) orowan intensification; (3) strengthening interface thermal mismatch; that is, due to thermal mismatch of HfC particles with the W-3Re matrix, prismatic punch dislocations occur at the HfC/W-3Re interface, resulting in work hardening of the W-3Re matrix. The relationship between three different strengthening mechanisms and the mass content and the high-temperature strength of HfC in the tungsten-rhenium alloy is researched, and the results are as follows:
(1) grain refinement and strengthening
With the increase of the mass content of HfC in the tungsten-rhenium alloy, the grain size of the tungsten-rhenium alloy matrix is obviously refined, the high-temperature strength of the tungsten-rhenium alloy is enhanced according to the Hall-Petch relation, and the contribution value delta sigma GR of the grain refinement and reinforcement to the high-temperature strength of the tungsten-rhenium alloy is estimated by the formula (1):
wherein K in the formula (1) is a constant, dcAnd dmAverage grain sizes of the tungsten-rhenium alloy and the reference sample, respectively;
(2) orowan enhancement
In the metal matrix composite material, HfC, La2O3TiC, and the like, in-situ or ex-situ reinforcing particles reinforce the metal matrix by inhibiting dislocation motion. During plastic deformation, as dislocations in the tungsten-rhenium alloy matrix interact with dispersed HfC, the dislocations tend to bow out and form Orowan rings for strengthening, and the contribution value of the Orowan strengthening to the high-temperature strength of the tungsten-rhenium alloy, Delta sigma HfC, is calculated by the formula (2):
wherein M in formula (1) is Taylor factor, G is shear modulus (161GPa), b is size of Burgers vector (0.274nm),
for the HfC particle diameter, λ is the interparticle distance of HfC particles in the tungsten-rhenium alloy matrix, and the interparticle distance λ of HfC particles is calculated by equation (3):
wherein, VHfCIs the volume fraction of HfC;
(3) interfacial thermal mismatch enhancement
HfC particles (6.7-7 x 10)-6K-1) With W-Re substrate (5.43X 10)-6K-1) The thermal mismatch causes prismatic punching of HfC-W interface dislocation, causes work hardening of the metal matrix composite, and enhances the interface thermal mismatch to the high temperature of the tungsten-rhenium alloyThe contribution value Δ σ TM of the intensity is calculated by equation (4):
wherein K is the material constant 0.94, G is the shear modulus 161GPa, b is the Burgers vector 0.274nm, Δ T is the difference between the processing temperature and the testing temperature, Δ C is the difference in CTE, V is the difference between the processing temperature and the testing temperatureHfCVolume fraction of HfC in the matrix, dHfCTo enhance the HfC particle diameter.
In the tungsten-rhenium alloys prepared in the embodiments 1-4 and the comparative example 1 of the invention, the strengthening mechanisms are applied to the high-temperature strength (the high temperature is 1500 ℃, the deformation is 50%, and the strain rate is 0.1 s)-1) The contribution of (c) is shown in table 2.
TABLE 2
As can be seen from table 2, as the mass content of HfC in the tungsten-rhenium alloy increases, the experimental compressive yield strength of the tungsten-rhenium alloy also increases, wherein as the mass content of HfC in the tungsten-rhenium alloy increases, the contribution value of the grain refinement strengthening mechanism to the high-temperature strength of the tungsten-rhenium alloy is significantly increased, and the contribution ratio is significantly increased; however, as the mass content of HfC in the tungsten-rhenium alloy is increased, the contribution value of the Orowan strengthening mechanism to the high-temperature strength of the tungsten-rhenium alloy is increased and then reduced, and the contribution ratio is obviously reduced, which shows that as the mass content of HfC is increased, HfC particles begin to agglomerate, and the strengthening effect of Orowan is inevitably weakened; with the increase of the mass content of HfC in the tungsten-rhenium alloy, the contribution value of an interface thermal mismatch strengthening mechanism to the high-temperature strength of the tungsten-rhenium alloy is gradually increased, and the contribution ratio is increased, which shows that HfC remarkably improves the punching effect of HfC/W-Re interface dislocation.
In conclusion, the strengthening mechanism for improving the high-temperature strength of the tungsten-rhenium alloy is as follows: (1) grain refinement and reinforcement; (2) orowan intensification; (3) the three strengthening mechanisms have different influences on the microstructure and the mechanical property of the tungsten-rhenium alloy, and the relationship between the three strengthening mechanisms and the HfC mass content in the tungsten-rhenium alloy is different and needs to be considered simultaneously.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modification, change and equivalent changes of the above embodiments according to the technical essence of the invention are still within the protection scope of the technical solution of the invention.
Claims (8)
1. A method for improving the high-temperature strength of a tungsten-rhenium alloy is characterized by comprising the following steps:
firstly, accurately weighing W powder, Re powder and HfC powder according to the component contents of elements in the tungsten-rhenium alloy, and carrying out high-energy ball milling in an inert atmosphere to obtain mixed alloy powder;
step two, the mixed alloy powder obtained in the step one is put into a graphite die for rapid discharge plasma sintering, and the tungsten-rhenium alloy is obtained after furnace cooling; the rapid discharge plasma sintering process comprises the following steps: under the pressure condition of 30-60 MPa, the temperature is firstly increased to 1200 ℃ at the speed of 20 ℃/min, then is increased to 2400 ℃ at the speed of 5 ℃/min, and is kept for 25-35 min.
2. The method for improving the high-temperature strength of the tungsten-rhenium alloy as claimed in claim 1, wherein in the first step, the mass purity of the W powder is 99.9%, the average grain diameter is 5 μm, the mass purity of the Re powder is 99.95%, the average grain diameter is 2 μm, the mass purity of the HfC powder is 99.9%, and the average grain diameter is 1 μm.
3. The method for improving high-temperature strength of the tungsten-rhenium alloy according to claim 1, wherein in the first step, the high-energy ball milling is performed by a QM-3SP2 planetary ball mill, an agate jar is adopted, grinding balls are agate balls, the rotation speed of the high-energy ball milling is 350-450 rpm, the time is 35-45 h, and the ball-to-material ratio is 10-15: 1.
4. the method for improving the high-temperature strength of the tungsten-rhenium alloy as claimed in claim 1, wherein in the step one, absolute ethyl alcohol is added as a control agent during the high-energy ball milling, and the addition amount of the control agent is 10-20% of the total mass of the W powder, the Re powder and the HfC powder.
5. The method for improving high-temperature strength of the tungsten-rhenium alloy according to claim 1, wherein in the step one, the mixed alloy powder is cleaned with absolute ethyl alcohol for 2-3 times after the high-energy ball milling is finished, the mass of the absolute ethyl alcohol used for cleaning is 5-10 times of the total mass of the W powder, the Re powder and the HfC powder, the cleaned mixed alloy powder is subjected to vacuum drying, the temperature of the vacuum drying is 40-60 ℃, and the drying time is 3-5 hours.
6. The method for improving the high-temperature strength of the tungsten-rhenium alloy as claimed in claim 1, wherein in the second step, graphite paper is laid on the inner surface of the graphite mold, then the mixed alloy powder is filled in the graphite mold, and the graphite mold is fixed outside the graphite mold by a carbon fiber mold.
7. The method for improving the high-temperature strength of the tungsten-rhenium alloy as claimed in claim 1, wherein argon is introduced for protection during the rapid discharge plasma sintering in the second step, and the tungsten-rhenium alloy is discharged after being cooled to room temperature along with the furnace.
8. The method for improving the high-temperature strength of the tungsten-rhenium alloy as claimed in claim 1, wherein the composition of the tungsten-rhenium alloy in the second step is W-3Re-xHfC, wherein the mass content of W is 97%, the mass content of Re is 3%, the mass content of HfC is x% of the total mass of W and Re, and 0 < x ≦ 10.
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