CN114559040A - Aluminum-containing self-passivated tungsten alloy and preparation method and application thereof - Google Patents
Aluminum-containing self-passivated tungsten alloy and preparation method and application thereof Download PDFInfo
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- 229910001080 W alloy Inorganic materials 0.000 title claims abstract description 42
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 38
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 44
- 239000000956 alloy Substances 0.000 claims abstract description 44
- 230000003647 oxidation Effects 0.000 claims abstract description 28
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 28
- 239000000843 powder Substances 0.000 claims abstract description 25
- 238000002161 passivation Methods 0.000 claims abstract description 22
- 239000011159 matrix material Substances 0.000 claims abstract description 10
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 6
- 238000005551 mechanical alloying Methods 0.000 claims abstract description 6
- 238000000498 ball milling Methods 0.000 claims description 36
- 125000004122 cyclic group Chemical group 0.000 claims description 15
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- 239000000463 material Substances 0.000 claims description 13
- 238000002490 spark plasma sintering Methods 0.000 claims description 9
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- 230000004927 fusion Effects 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims 1
- 239000011651 chromium Substances 0.000 abstract description 18
- 229910052721 tungsten Inorganic materials 0.000 abstract description 14
- 238000005245 sintering Methods 0.000 abstract description 12
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 abstract description 12
- 239000010937 tungsten Substances 0.000 abstract description 12
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 5
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- 238000012360 testing method Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 3
- 238000005275 alloying Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
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- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
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- 206010061592 cardiac fibrillation Diseases 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- QDOXWKRWXJOMAK-UHFFFAOYSA-N chromium(III) oxide Inorganic materials O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 1
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- 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
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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
- 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
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- 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
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- 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
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- 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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Abstract
The invention provides an aluminum-containing self-passivation tungsten alloy and a preparation method and application thereof. Furthermore, the mass percent content of the passivation element Cr is 2-12%, and the mass percent content of the passivation element Al is 1-3%. The self-passivating tungsten alloy is prepared by performing discharge plasma sintering after alloy powder is obtained by mechanical alloying. According to the invention, a certain amount of chromium and aluminum are added into the tungsten matrix as passivation elements, so that the oxidation resistance is obviously improved, the stability is also improved, and the tungsten alloy can adapt to a harsher application environment.
Description
Technical Field
The invention relates to the field of self-passivation tungsten alloys, in particular to an aluminum-containing self-passivation tungsten alloy and a preparation method and application thereof.
Background
Tungsten, due to its high hardness, melting point and low physical sputtering properties, is widely used in military applicationsThe fields of aerospace, nuclear fusion and the like. In particular in the field of nuclear fusion, tungsten is considered as a prime candidate for divertors and the first wall facing the plasma. But divertors and plasma-facing first wall materials need to withstand low energy ions for long periods of time: (<100eV), high heat flow (10 to 20 MW/m)2) Strong beam current (10)22～1024m-2·s-1) Energy damage caused by electromagnetic radiation, high-energy fusion neutron irradiation and the like. In particular, in the event of Loss-of-cooling (LOCA) caused by human or natural factors, air and water vapour enter the vacuum chamber, bringing the temperature in the container to above 1000 ℃ within a few days and maintaining it at this temperature for about two months. However, tungsten is easy to oxidize, and the oxidation is obviously accelerated at the high temperature of over 500 ℃ and the middle temperature, and cracks are generated; at temperatures above 1000 deg.C, tungsten oxidizes to volatile WO3Not only can cause environmental pollution, but also can cause a fatal accident which is difficult to predict when the device fails. In a nuclear fusion reactor, tungsten also has combined action of hydrogen helium effect and fibrillation effect, so that the performance of the material is greatly reduced, and surface cracking and embrittlement are caused. Therefore, how to improve the high temperature oxidation resistance of the self-passivated tungsten alloy becomes the current research hotspot.
At present, the improvement of the oxidation resistance of tungsten mainly comprises two approaches of preparing a coating on the surface of the alloy and adding alloying elements. The limited thickness of the coating can not meet the requirement of long-time oxidation resistance, and the difference of the thermal expansion coefficients of the coating and the substrate can cause the coating to generate cracks and holes, and the defects become channels for oxygen to diffuse into the tungsten substrate so as to oxidize the tungsten substrate. Alloying can effectively avoid the defects, so that the preparation of the self-passivated tungsten alloy through mechanical alloying and powder metallurgy becomes a main way and method for improving the oxidation resistance of tungsten.
In recent years, researchers design and prepare self-passivation tungsten alloy taking Cr as passivation element to improve the high-temperature oxidation performance of tungsten, but the oxidation resistance at high temperature still needs to be further improved, for example, W98% -Cr 2% alloy is circularly oxidized for 15 hours at 900 ℃, and the mass per unit area is increased by more than 175mg/cm2。
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides an aluminum-containing self-passivation tungsten alloy, which realizes the obvious improvement of oxidation resistance by adding chromium and aluminum as passivation elements in a tungsten matrix.
The invention also provides a preparation method and application of the aluminum-containing self-passivation tungsten alloy.
The invention provides an aluminum-containing self-passivated tungsten alloy which comprises a matrix element W, passivation elements Cr and Al.
The invention adds the passivating element Al on the basis of the prior self-passivating tungsten alloy taking Cr as the passivating element, and the passivating element is preferentially oxidized at high temperature, wherein Al2O3Has stability superior to that of Cr2O3And a continuous and compact protective film is formed on the surface of the alloy, so that the alloy matrix is protected.
According to the aluminum-containing self-passivated tungsten alloy provided by the specific embodiment of the invention, the mass percent of the passivated element Cr is 2-12%, and the mass percent of the passivated element Al is 1-3%. More preferably, the content of the passivation element Cr is 2-8% by mass, and the content of the passivation element Al is 1% by mass.
In a specific embodiment of the invention, in the aluminum-containing self-passivated tungsten alloy, the mass percentage content of the matrix element W is 97%, the mass percentage content of the passivation element Cr is 2%, and the mass percentage content of the passivation element Al is 1%.
In another specific embodiment of the invention, in the aluminum-containing self-passivated tungsten alloy, the mass percentage content of the matrix element W is 91%, the mass percentage content of the passivation element Cr is 8%, and the mass percentage content of the passivation element Al is 1%.
The density of the aluminum-containing self-passivated tungsten alloy is more than 98%, the hardness is more than 840HV, and the grain size is less than 1.2 mu m.
After the aluminum-containing self-passivated tungsten alloy is cyclically oxidized for 15 hours at 900 ℃, the increase of the mass per unit area is not more than 104mg/cm2. One of the circulation is oxidation for 0.5h, and the mixture is taken out and cooled to room temperature in the airI.e. cyclic oxidation 15h comprises 30 cycles.
After the aluminum-containing self-passivated tungsten alloy is cyclically oxidized for 15 hours at 800 ℃, the mass per unit area is increased by not more than 2mg/cm2。
In a specific embodiment of the present invention, the following method may be used for the oxidation resistance test:
and removing oxide skin on the surface of the sintered alloy block on a grinding and polishing machine, and linearly cutting the sintered alloy block into blocks of 5 multiplied by 3 mm. The cut block was polished to 1 μm and ultrasonically cleaned for 30 min. The cleaned blocks are placed in a crucible for weighing, and then the crucible and the alloy blocks are placed in a muffle furnace together for carrying out a cyclic oxidation experiment at 800-900 ℃. Samples were taken every half hour and allowed to cool to room temperature in air, their mass changes were measured on a sensitive balance and recorded, and the cyclic oxidation was stopped for 15h (30 cycles).
The invention also provides a preparation method of the aluminum-containing self-passivation tungsten alloy.
The preparation method provided by the invention comprises the step of carrying out spark plasma sintering after obtaining alloy powder by adopting mechanical alloying.
According to an embodiment of the present invention, the conditions of the spark plasma sintering include: the temperature is 1400 ℃ and 1600 ℃, the pressure is 40-50Mpa, and the time is 1-5 min.
In one embodiment of the present invention, when a columnar alloy ingot having a size of about 20mm in diameter and 6.5mm in height is prepared by Spark Plasma Sintering (SPS), the specific sintering parameters are 1500 ℃ at a pressure of 45MPa for 3 min.
According to the specific implementation mode of the invention, the mechanical alloying is a ball milling mode, the ball-material ratio is 5:1-10:1, the ball milling rotation speed is 350-450r/min, and the ball milling time is 35-50 h.
According to the embodiment of the invention, the agglomerated powder is ground and sieved periodically during the ball milling process. Wherein grind and sieve and go on in the glove box, grind the invalid ball-milling that sieves that can avoid the powder to glue the jar and lead to caking powder.
In one embodiment of the present invention, the preparation method comprises the steps of:
(1) taking powder according to a ball-material ratio of 5:1-10:1, mixing W, Cr and Al powder according to the weight ratio of W: cr: al 97: 2: 1 (wt%) are mixed evenly and put into a ball milling pot;
(2) placing the mixed powder obtained in the step (1) in a planetary ball mill for ball milling for 35-50h, periodically taking down a ball milling tank in the ball milling process, placing the ball milling tank in a glove box, and continuing ball milling after grinding and sieving the agglomerated powder to avoid invalid ball milling caused by powder sticking to the tank;
(3) weighing a certain amount of the alloy powder obtained in the step (2), preparing a columnar alloy block through Spark Plasma Sintering (SPS), wherein the sintering parameters are as follows: the temperature is 1400-1600 ℃, the pressure is 40-50Mpa, and the time is 1-5 min.
Among them, W, Cr and Al powders preferably have a purity of 99.9% or more and a particle diameter of 1 to 3 μm.
The invention also provides application of the aluminum-containing self-passivated tungsten alloy in jet pipe materials at the tail of an aeroengine, divertors of nuclear fusion and plasma-oriented materials.
The invention provides an aluminum-containing self-passivation tungsten alloy and a preparation method and application thereof.
Drawings
FIG. 1 is a SEM image of microstructure of various alloys, wherein (a) W-2Cr (b) W-2Cr-1Al (c) W-8Cr-1 Al;
FIG. 2 is a graph of mass gain per unit area for W-2Cr, W-2Cr-1Al and W-8Cr-1Al alloys by cyclic oxidation at 800 ℃ for 15 hours;
FIG. 3 is an SEM image of the surface of different alloys subjected to cyclic oxidation at 800 ℃ for 15h, wherein (a) W-2Cr (b) W-2Cr-1Al (c) W-8Cr-1 Al;
FIG. 4 is a SEM image of a cross section of various alloys subjected to cyclic oxidation at 800 ℃ for 15h, wherein (a) W-2Cr (b) W-2Cr-1Al (c) W-8Cr-1 Al;
FIG. 5 is a graph of mass gain per unit area for W-2Cr and W-2Cr-1Al alloys cyclically oxidized at 900 ℃ for 15 hours.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Unless defined otherwise, technical or scientific terms used herein shall have the ordinary meaning as understood by one of ordinary skill in the art to which this invention belongs. The examples do not show the specific techniques or conditions, according to the technical or conditions described in the literature in the field, or according to the product specifications.
The materials and reagents used in the following examples are all available from normal commercial sources unless otherwise specified.
Example 1
The embodiment provides an aluminum-containing self-passivated tungsten alloy, which is prepared by the following steps:
(1) taking powder according to a ball-material ratio of 5:1, mixing pure W, pure Cr and pure Al powder with the purity of 99.9 percent and the particle size of 1-3 mu m according to the weight ratio of W: cr: al 97: 2: 1 (wt.%) were mixed well and placed in a ball mill jar, all in a glove box.
(2) The ball milling tank is placed on a planetary ball mill to perform ball milling for 40 hours at a speed of 400r/min, the ball milling tank is taken down and placed in a glove box when the ball milling time is respectively 1 hour, 3 hours, 5 hours, 10 hours, 20 hours, 30 hours and 40 hours, the agglomerated powder is ground and sieved, and then ball milling is continued, and the step is mainly used for preventing invalid ball milling.
(3) Weighing 40g of powder subjected to ball milling for 40h, and preparing a columnar block with the diameter of 20mm and the height of 6.5mm by using discharge plasma sintering (SPS), wherein the specific sintering process comprises the steps of keeping the temperature at 1500 ℃ and the pressure at 45MPa for 3min to obtain the aluminum-containing self-passivated tungsten alloy, which is recorded as W-2Cr-1 Al.
Example 2
The embodiment provides an aluminum-containing self-passivated tungsten alloy, which is prepared by the following steps:
(1) taking powder according to a ball-material ratio of 5:1, mixing pure W, pure Cr and pure Al powder with the purity of 99.9 percent and the particle size of 1-3 mu m according to the weight ratio of W: cr: al 91: 8: 1 (wt.%) were mixed well and placed in a ball mill jar, all in a glove box.
(2) The ball milling tank is placed on a planetary ball mill to be ball milled for 40 hours at a speed of 400r/min, the ball milling tank is taken down and placed in a glove box when the ball milling time is respectively 1 hour, 3 hours, 5 hours, 10 hours, 20 hours, 30 hours and 40 hours, the agglomerated powder is ground and sieved, and then ball milling is continued, and the step is mainly to prevent invalid ball milling.
(3) Weighing 40g of powder subjected to ball milling for 40h, and preparing a columnar block with the diameter of 20mm and the height of 6.5mm by using discharge plasma sintering (SPS), wherein the specific sintering process comprises the steps of keeping the temperature at 1500 ℃ and the pressure at 45MPa for 3min to obtain the aluminum-containing self-passivated tungsten alloy, which is recorded as W-8Cr-1 Al.
Comparative example 1
The comparative example provides a self-passivating tungsten alloy, the method of preparation is as follows:
(1) taking powder according to the ball-material ratio of 5:1, mixing pure W and pure Cr powder with the purity of 99.9 percent and the particle size of 1-3 mu m according to the weight ratio of W: 98% of Cr: 2 percent (wt%) are mixed evenly and placed in a ball milling tank, and the operations are carried out in a glove box.
(2) The ball milling tank is placed on a planetary ball mill to perform ball milling for 40 hours at a speed of 400r/min, the ball milling tank is taken down and placed in a glove box when the ball milling time is respectively 1 hour, 3 hours, 5 hours, 10 hours, 20 hours, 30 hours and 40 hours, the agglomerated powder is ground and sieved, and then ball milling is continued, and the step is mainly used for preventing invalid ball milling.
(3) Weighing 40g of powder subjected to ball milling for 40h, and preparing a columnar block with the diameter of 20mm and the height of 6.5mm by using discharge plasma sintering (SPS), wherein the specific sintering process comprises the steps of keeping the temperature at 1500 ℃ and the pressure at 45MPa for 3min to obtain the self-passivation tungsten alloy, which is recorded as W-2 Cr.
Performance testing
1. Density, hardness testing and microstructure observation
And removing oxide skin on the surface of the columnar block obtained by sintering on a grinding and polishing machine, and linearly cutting into blocks of 3 multiplied by 6 mm. The cut block was polished to 1 μm and ultrasonically cleaned for 30 min. The cleaned block was subjected to density and hardness tests, and the microstructure thereof was observed.
As a result: the density of the W-2Cr alloy is 96.53 percent, the hardness is 721.1 +/-23.8 HV, and the grain size is about 1.37 +/-0.09 mu m;
the density of the W-2Cr-1Al alloy is 98.07 percent, the hardness is 847.3 +/-19.8 HV, and the grain size is about 0.99 +/-0.11 mu m;
the density of the W-8Cr-1Al alloy is 97.64%, the hardness is 1096.8 +/-37.3 HV, and the grain size is about 0.80 +/-0.09 mu m.
FIG. 1 is a SEM image of the microstructure of W-2Cr, W-2Cr-1Al and W-8Cr-1Al alloys.
As can be seen from the above, the density and hardness of the W-2Cr-1Al alloy are improved and the grain size is reduced compared with the W-2Cr alloy, which indicates that Al is formed after Al is added2O3The dispersed phase inhibits the growth of crystal grains and plays a role in dispersion strengthening and fine grain strengthening.
Compared with W-2Cr-1Al alloy, the W-8Cr-1Al alloy has smaller density difference, increased hardness and reduced grain size, and shows that the dispersion strengthening effect and the fine grain strengthening effect are more obvious.
2. Oxidation resistance test at 800 deg.C
And removing oxide skin on the surface of the columnar block obtained by sintering on a grinding and polishing machine, and linearly cutting into blocks of 5 multiplied by 3 mm. The cut block was polished to 1 μm and ultrasonically cleaned for 30 min. The cleaned blocks are placed in a crucible and weighed, and then the crucible and the alloy blocks are placed into a muffle furnace together to carry out a cyclic oxidation experiment at 800 ℃. Samples were taken every half hour and allowed to cool to room temperature in air, their mass changes were measured on a sensitive balance and recorded, and the cyclic oxidation was stopped for 15h (30 cycles). Three parallel experiments were performed for each sample and the average mass change was calculated for each cycle.
FIG. 2 is a graph showing the mass increase per unit area of W-2Cr, W-2Cr-1Al and W-8Cr-1Al alloys by cyclic oxidation at 800 ℃ for 15h (30 cycles), the mass increase per unit area of the W-2Cr-1Al alloys being about 11.4 times lower than that of the W-2Cr alloys. The increase in mass per unit area of the W-8Cr-1Al alloy is slightly lower than that of the W-2Cr-1Al alloy.
SEM images of surfaces subjected to cyclic oxidation at 800 ℃ for 15h (30 cycles) are shown in FIG. 3, wherein only tiny small pits appear on the oxidized surface of the W-2Cr-1Al alloy, only tiny bumps appear on the surface of the W-8Cr-1Al alloy, and obvious bumps appear on the oxidized surface of the W-2Cr alloy and are accompanied by cracks.
As shown in the SEM image of the cross section of the alloy subjected to cyclic oxidation at 800 ℃ for 15h (30 cycles), the thickness of the oxide layer of the W-2Cr-1Al alloy was about 10.8 μm, the thickness of the oxide layer of the W-8Cr-1Al alloy was about 3.8 μm, and the thickness of the oxide layer of the W-2Cr alloy was about 117.8. mu.m.
3. 900 ℃ antioxidation performance test
And removing oxide skin on the surface of the columnar block obtained by sintering on a grinding and polishing machine, and linearly cutting into blocks of 5 multiplied by 3 mm. The cut block was polished to 1 μm and ultrasonically cleaned for 30 min. The cleaned blocks were weighed in a crucible, and then the crucible and the alloy blocks were placed together in a muffle furnace for cyclic oxidation experiments at 900 ℃. Samples were taken every half hour and allowed to cool to room temperature in air, their mass changes were measured on a sensitive balance and recorded, and the cyclic oxidation was stopped for 15h (30 cycles). Three parallel experiments were performed for each sample and the average mass change was calculated for each cycle.
FIG. 5 is a graph showing the mass increase per unit area of W-2Cr and W-2Cr-1Al alloys by cyclic oxidation at 900 ℃ for 15 hours (30 cycles), and the mass increase per unit area of the W-2Cr-1Al alloys is significantly lower than that of the W-2Cr sum.
The above experimental results can show that the oxidation resistance of the self-passivated tungsten alloy can be obviously improved after Al is added, and the Al is preferentially oxidized to form continuous and compact Al2O3And the protective film inhibits oxygen anions from entering the alloy matrix, thereby playing a role in protecting the alloy matrix.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. An aluminum-containing self-passivated tungsten alloy is characterized by comprising a matrix element W and passivation elements Cr and Al.
2. The aluminum-containing self-passivating tungsten alloy of claim 1, wherein the passivating element Cr is present in an amount of 2-12% by mass and the passivating element Al is present in an amount of 1-3% by mass.
3. The aluminum-containing self-passivating tungsten alloy of claim 2, wherein in the aluminum-containing self-passivating tungsten alloy, the mass percent content of the matrix element W is 97%, the mass percent content of the passivating element Cr is 2%, and the mass percent content of the passivating element Al is 1%.
4. The aluminum-containing self-passivating tungsten alloy of claim 2 or 3, wherein the aluminum-containing self-passivating tungsten alloy has a density of greater than 98%, a hardness of greater than 840HV, and a grain size of less than 1.2 μm.
5. The aluminum-containing self-passivating tungsten alloy of claim 4, wherein the aluminum-containing self-passivating tungsten alloy has a mass increase per unit area of not more than 104mg/cm after cyclic oxidation at 900 ℃ for 15 hours2。
6. The process for the preparation of an aluminium-containing self-passivating tungsten alloy according to any of claims 1 to 5, comprising the step of spark plasma sintering after obtaining the alloy powder by mechanical alloying.
7. The method of preparing an aluminum-containing self-passivating tungsten alloy of claim 6, wherein the conditions of the spark plasma sintering include: the temperature is 1400 ℃ and 1600 ℃, the pressure is 40-50Mpa, and the time is 1-5 min.
8. The method as claimed in claim 6, wherein the mechanical alloying is ball milling, the ball/material ratio is 5:1-10:1, the ball milling rotation speed is 350-.
9. The method for preparing the self-passivating tungsten alloy containing aluminum according to claim 8, wherein the agglomerated powder is ground and sieved periodically during the ball milling process.
10. Use of the aluminum-containing self-passivating tungsten alloy of any of claims 1-5 in aircraft engine tail nozzle materials as well as diverters and plasma-facing materials for nuclear fusion.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1086708A (en) * | 1966-02-01 | 1967-10-11 | Gen Electric Co Ltd | Improvements in or relating to metal bodies and their manufacture |
| JP2004169148A (en) * | 2002-11-21 | 2004-06-17 | Allied Material Corp | Tungsten alloy having oxidation resistance, and production method therefor |
| JP2006097068A (en) * | 2004-09-29 | 2006-04-13 | Allied Material Corp | Tungsten alloy having oxidation resistance, and production method therefor |
| CN107299269A (en) * | 2017-06-12 | 2017-10-27 | 合肥工业大学 | A kind of W Cr Al composites of resistance to high temperature oxidation and preparation method thereof |
| CN109778042A (en) * | 2019-01-24 | 2019-05-21 | 中南大学 | A kind of high intensity tungsten based alloy and preparation method thereof |
| CN111334695A (en) * | 2020-03-09 | 2020-06-26 | 合肥工业大学 | High-density nano W alloy with good self-passivation behavior and preparation method thereof |
-
2022
- 2022-03-08 CN CN202210220897.3A patent/CN114559040A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1086708A (en) * | 1966-02-01 | 1967-10-11 | Gen Electric Co Ltd | Improvements in or relating to metal bodies and their manufacture |
| JP2004169148A (en) * | 2002-11-21 | 2004-06-17 | Allied Material Corp | Tungsten alloy having oxidation resistance, and production method therefor |
| JP2006097068A (en) * | 2004-09-29 | 2006-04-13 | Allied Material Corp | Tungsten alloy having oxidation resistance, and production method therefor |
| CN107299269A (en) * | 2017-06-12 | 2017-10-27 | 合肥工业大学 | A kind of W Cr Al composites of resistance to high temperature oxidation and preparation method thereof |
| CN109778042A (en) * | 2019-01-24 | 2019-05-21 | 中南大学 | A kind of high intensity tungsten based alloy and preparation method thereof |
| CN111334695A (en) * | 2020-03-09 | 2020-06-26 | 合肥工业大学 | High-density nano W alloy with good self-passivation behavior and preparation method thereof |
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