CN111020259A - Flaky intermetallic compound reinforced fine-grain tungsten alloy and preparation method thereof - Google Patents
Flaky intermetallic compound reinforced fine-grain tungsten alloy and preparation method thereof Download PDFInfo
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- 229910000765 intermetallic Inorganic materials 0.000 title claims abstract description 54
- 229910001080 W alloy Inorganic materials 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 81
- 238000005245 sintering Methods 0.000 claims abstract description 68
- 238000000034 method Methods 0.000 claims abstract description 59
- 238000000498 ball milling Methods 0.000 claims abstract description 54
- 238000011065 in-situ storage Methods 0.000 claims abstract description 26
- 230000003647 oxidation Effects 0.000 claims abstract description 25
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 23
- 239000002131 composite material Substances 0.000 claims abstract description 19
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002245 particle Substances 0.000 claims abstract description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims description 26
- 230000008569 process Effects 0.000 claims description 26
- 238000004321 preservation Methods 0.000 claims description 16
- 238000000713 high-energy ball milling Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 9
- 229910001005 Ni3Al Inorganic materials 0.000 claims description 7
- 238000002490 spark plasma sintering Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- 229910017372 Fe3Al Inorganic materials 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000011812 mixed powder Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000013078 crystal Substances 0.000 abstract description 9
- 239000007791 liquid phase Substances 0.000 abstract description 5
- 229910052721 tungsten Inorganic materials 0.000 abstract description 5
- 239000010937 tungsten Substances 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 4
- 229910045601 alloy Inorganic materials 0.000 description 15
- 239000000956 alloy Substances 0.000 description 15
- 229910000838 Al alloy Inorganic materials 0.000 description 10
- 239000012071 phase Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 238000005452 bending Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 6
- 230000035515 penetration Effects 0.000 description 5
- 229910000711 U alloy Inorganic materials 0.000 description 4
- 238000005728 strengthening Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 229910003271 Ni-Fe Inorganic materials 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000000875 high-speed ball milling Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 235000001674 Agaricus brunnescens Nutrition 0.000 description 1
- 229910000967 As alloy Inorganic materials 0.000 description 1
- 229910021330 Ti3Al Inorganic materials 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000003904 radioactive pollution Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002277 temperature effect Effects 0.000 description 1
- 239000002699 waste material Substances 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
- C22C1/045—Alloys based on refractory metals
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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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- 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
- C22C1/047—Making non-ferrous alloys by powder metallurgy comprising intermetallic compounds
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/10—Alloys containing non-metals
- C22C1/1078—Alloys containing non-metals by internal oxidation of material in solid state
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- 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
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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
- B22F2003/1051—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding by electric discharge
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Abstract
The invention belongs to the technical field of tungsten alloy, and discloses a flaky intermetallic compound reinforced fine-grained tungsten alloy and a preparation method thereof. Firstly, changing the diameter-thickness ratio of intermetallic compound raw material powder by different ball milling methods and processes to obtain tungsten alloy composite powder which contains flaky intermetallic compounds and is uniformly mixed; then, carrying out in-situ oxidation treatment on the original powder to enable the surface of the flaky intermetallic compound powder to generate nano alumina particles by self; and finally, performing one-step or two-step discharge plasma sintering on the obtained tungsten alloy composite powder to finally prepare the flaky intermetallic compound reinforced fine-grained tungsten alloy. The invention overcomes the defects of longer period, larger tungsten crystal grain, lower mechanical property and the like of the traditional liquid phase sintering mode, and the prepared tungsten alloy has the characteristics of uniform structure, fine crystal grain, high relative density and the like, and the comprehensive mechanical property is also obviously improved.
Description
Technical Field
The invention belongs to the technical field of tungsten alloy, and particularly relates to a flaky intermetallic compound reinforced fine-grained tungsten alloy and a preparation method thereof.
Background
Tungsten alloy is widely used as a substitute material of radioactive pollution depleted uranium armor-piercing bullet due to a series of excellent performances such as high density, high strength and good machinability. However, the traditional tungsten alloy bullet core material represented by W-Ni-Fe alloy has the problem of insensitive heat insulation and shearing property, and the problem also causes the formation of mushroom head and the reduction of the penetration depth in the penetration process. The main factors that can improve the adiabatic shear of the alloy include lower thermal conductivity, higher alloy hardness, and finer tungsten grain size. Therefore, the research and development of the novel tungsten alloy meeting the characteristics have important significance for improving the self-sharpening effect of the kinetic energy penetrator of the tungsten alloy, improving the penetration power of the tungsten alloy to the penetration level not lower than that of the depleted uranium alloy and further completely replacing the depleted uranium alloy.
Ni3Al、Fe3Al、Ti3Intermetallic compounds such as Al have the advantages of low thermal conductivity, high hardness, low solubility for tungsten, and the like. Due to Ni3Al and the like have thermal conductivity close to that of depleted uranium alloys and lower thermal diffusivity, which makes them have adiabatic shear behavior similar to that of depleted uranium alloys. The lower solubility to tungsten may hinder the dissolution re-precipitation process during liquid phase sintering and eventually refine the tungsten grain size. In addition, Ni3The yield strength of Al has a positive temperature effect below the peak temperature, and the material softens rapidly when the temperature exceeds the peak temperature, and this effect also helps to initiate adiabatic shear behavior. When used as a bullet, it is competitive with uranium-depleted bullets because it is self-sharpening without reducing its penetration depth. But recently the prepared W- (Ni/Fe/Ti) was investigated3The mechanical property of the Al alloy is still a certain gap compared with the traditional W-Ni-Fe alloy. At present, common methods for improving the performance of tungsten alloy mainly comprise adding additives, changing a sintering process, introducing second-phase reinforcement and the like, but the methods have the problems of precious metal waste, complex process, poor bonding of an added phase interface, uneven dispersion and the like. Recently, microstructure design is considered as an effective strategy for improving the mechanical properties of the alloy, and particularly, the design of the lamellar structure composite material can improve the ductility and toughness of the alloy by controlling the propagation mode of cracks so as to avoid sudden failure of the material. Therefore, by a novel microstructure design method to obtain W- (Ni/Fe/Ti) with good overall properties3Al alloys have become a problem requiring urgent research.Therefore, to meet the increasing demand for new high performance tungsten alloys, we propose a new sheet (Ni/Fe/Ti)3Al intermetallic compound reinforced fine-grain tungsten alloy and a preparation method thereof.
The patent develops a brand new technical route of enhancing tungsten alloy by a microscopic layered structure, reasonably selects intermetallic compounds as novel tungsten alloy binding phases, regulates and controls the flaky morphology of intermetallic compound powder by setting different mixed material ball-milling processes and assists in-situ oxidation to regulate and control the autogenous Al on the surface of the intermetallic compound2O3The quantity and the shape of the particles further achieve the purpose of obtaining the flake (Ni/Fe/Ti) with good comprehensive mechanical property3The Al intermetallic compound enhances the purpose of the tungsten alloy. The invention overcomes the defects of the traditional strengthening method, has simple process and can be widely applied to strengthening of other alloys.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the invention aims to provide a preparation method of a flaky intermetallic compound reinforced fine-grained tungsten alloy. The preparation method overcomes the technical defects of high cost, complex flow, poor interface combination effect and the like of the traditional tungsten alloy reinforcement mode, and provides a method for simply and quickly preparing the fine-grained tungsten alloy with excellent performance.
Another object of the present invention is to provide a flake intermetallic compound reinforced fine grain tungsten alloy prepared by the above method.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a flaky intermetallic compound reinforced fine-grained tungsten alloy comprises the following preparation steps:
(1) mixing raw material tungsten powder and intermetallic compound powder according to a certain mass percentage; the intermetallic compound is Ni3Al、Fe3Al、Ti3At least one of Al;
(2) carrying out high-energy ball milling on the prepared raw material powder in a ball mill to obtain fine composite powder which contains flaky intermetallic compound powder and is uniformly mixed;
(3) carrying out in-situ oxidation treatment on the composite powder obtained in the step (2), and carrying out in-situ self-generation of nano alumina particles on the surface of the flaky intermetallic compound powder;
(4) and (4) performing discharge plasma sintering on the composite powder obtained in the step (3) to obtain the flaky intermetallic compound reinforced fine-grained tungsten alloy.
Further, in the step (1), the tungsten powder and intermetallic compound powder ingredients comprise the following components in percentage by mass: 85-95% of tungsten powder and 5-15% of intermetallic compound powder.
Further, the high-energy ball milling in the step (2) is performed by stirring ball milling, vibration ball milling or planetary ball milling.
Further, the high energy ball milling in the step (2) comprises a ball milling method together or a ball milling method separately; the ball milling method is to perform high-energy ball milling on the mixed powder of the tungsten powder and the intermetallic compound raw material together, and the ball milling method is to perform high-energy ball milling on the tungsten powder and the intermetallic compound powder respectively and then uniformly mix the two high-energy ball milling raw material powders through low-energy ball milling.
Further, the high-energy ball milling in the step (2) comprises one-step ball milling or two-step ball milling; the first-step ball milling is ball milling for 0-24 hours at a rotating speed of less than 1000r/min, and the second-step ball milling is ball milling at a low speed of less than 300r/min for 0-20 hours and then ball milling at a high speed of more than 300r/min for 0-4 hours.
Further, the in-situ oxidation treatment in the step (3) comprises room-temperature in-situ oxidation or low-temperature heat treatment in-situ oxidation; wherein the room-temperature in-situ oxidation time is 0-10 days; the temperature of the low-temperature heat treatment in-situ oxidation is 50-300 ℃, and the oxidation time is 0-24 h.
Further, the spark plasma sintering in the step (4) comprises a one-step sintering method or a two-step sintering method;
the process conditions of the one-step sintering method are as follows:
the sintering vacuum degree is less than 3Pa, the sintering temperature is 1350-1500 ℃, the sintering pressure is 30-100 MPa, the heating rate is 100-400 ℃/min, and the heat preservation time is 0-30 min;
the two-step sintering method comprises the following process conditions:
the first step is as follows: the sintering vacuum degree is less than 3Pa, the sintering temperature is 1000-1250 ℃, the sintering pressure is 30-100 MPa, the heating rate is 50-400 ℃/min, and the heat preservation time is 3-20 min;
the second step is that: the sintering vacuum degree is less than 3Pa, the sintering temperature is 1300-1400 ℃, the sintering pressure is 30-100 MPa, the heating rate is 200-400 ℃/min, and the heat preservation time is 0 min.
A flaky intermetallic compound reinforced fine-grained tungsten alloy is prepared by the method.
The principle of the invention is as follows: firstly, changing the diameter-thickness ratio of intermetallic compound raw material powder by different ball milling methods and processes to obtain tungsten alloy composite powder which contains flaky intermetallic compounds and is uniformly mixed; then, carrying out in-situ oxidation treatment on the original powder to enable the surface of the flaky intermetallic compound powder to generate nano alumina particles by self; and finally, performing one-step or two-step discharge plasma sintering on the obtained tungsten alloy composite powder to finally prepare the flaky intermetallic compound reinforced fine-grained tungsten alloy.
The preparation method and the obtained material have the following advantages and beneficial effects:
(1) the invention will (Ni/Fe/Ti)3The Al intermetallic compound binding phase is prepared into a flaky tungsten alloy reinforcing phase, a third heterogeneous phase is not introduced, the problem of an interface between a matrix and the reinforcing phase can be solved, the improvement of the comprehensive mechanical property of the tungsten alloy is facilitated, the cost is reduced, and the process is simplified.
(2) The invention makes full use of the characteristics of hot-pressing sintering, rapid heating, short-time heat preservation and the like of spark plasma sintering to prepare W- (Ni/Fe/Ti)3The Al alloy has the advantages of novel structure, higher density, fine crystal grains, higher hardness and the like, so that the self-sharpening property of the heat insulation shearing of the Al alloy can be improved compared with the traditional heavy tungsten alloy.
(3) The method utilizes in-situ oxidation to generate alumina particles on the surface of the sheet-shaped intermetallic compound and realizes the effect of synergistically enhancing the tungsten alloy with the sheet-shaped intermetallic compound. The mechanical property of the tungsten alloy is improved through microstructure regulation, and the consumption of precious resources by the traditional alloy element strengthening mode can be effectively avoided.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
A flake-form reinforced W-Ni of the present example3The rapid preparation method of the Al fine-grain alloy comprises the following steps and process conditions:
(1) the raw material components are proportioned as follows: with W, Ni3Al powder is used as an alloy raw material, and W90 percent and Ni are mixed according to the following mass percentage310 percent of Al. Purity of W powder>99.9％，Ni3Purity of Al powder>99％。
(2) Mixing the W powder and Ni3And putting the Al powder into a ball milling tank, and performing two-step ball milling and mixing on a planetary ball mill.
The two-step ball milling process is to perform low-speed ball milling for 18 hours at a rotating speed of 200 r/min. Then high-speed ball milling is carried out for 6h at 340 r/min. To obtain a fine composite powder containing a flaky intermetallic compound powder and uniformly mixed.
(3) And carrying out in-situ oxidation treatment on the uniformly mixed composite powder for 3 days at room temperature.
(4) And putting the powder into a graphite die, placing the graphite die into a heating cavity of a spark plasma sintering system, vacuumizing the graphite die, and performing spark plasma one-step sintering, wherein the sintering process conditions are that the sintering vacuum degree is less than 3Pa, the sintering pressure is 40MPa, the heating rate is 100 ℃/min, the sintering temperature is 1400 ℃, and the heat preservation time is 5 min.
By the preparation method, W-Ni with uniform tissue is obtained3The Al alloy has crystal grain less than 4 micron, relative density greater than 97%, macro hardness of 72.5HRA and bending strength of 959 MPa.
Example 2
A flake-form reinforced W-Ni of the present example3The rapid preparation method of the Al fine-grain heavy tungsten alloy comprises the following steps and process conditions:
(1) the raw material components are proportioned as follows: with W, Ni3Al powder is used as an alloy raw material and is calculated according to the following mass percentThe proportion of the ingredients W95% and Ni35 percent of Al. Purity of W powder>99.9％，Ni3Purity of Al powder>99％。
(2) Mixing the W powder and Ni3And (3) putting the Al powder into different ball milling tanks, performing one-step ball milling on the Al powder respectively on a vibration type ball mill, and then performing low-energy ball milling on the Al powder to uniformly mix the Al powder. The one-step ball milling process is to perform ball milling for 24 hours at the rotating speed of 340 r/min. To obtain a fine composite powder containing a flaky intermetallic compound powder and uniformly mixed.
(3) And carrying out low-temperature heat treatment and in-situ oxidation on the uniformly mixed composite powder. The low-temperature heat treatment temperature is 100 ℃, and the treatment time is 10 hours.
(4) The powder after the in-situ oxidation is filled into a graphite die and then is placed in a heating cavity of a spark plasma sintering system, the spark plasma two-step sintering is carried out after the vacuum pumping, and the sintering process conditions are as follows: the sintering vacuum degree is less than 3Pa, the sintering temperature is 1250 ℃, the sintering pressure is 40MPa, the heating rate is 100 ℃/min, and the heat preservation time is 5 min. The second step is that: the sintering vacuum degree is less than 3Pa, the sintering temperature is 1320 ℃, the sintering pressure is 50MPa, the heating rate is 200 ℃/min, and the heat preservation time is 0 min.
By the preparation method, W-Ni with uniform tissue is obtained3The Al alloy has crystal grain less than 3 micron, relative density greater than 96%, macro hardness 73.5HRA and bending strength 875 MPa.
Example 3
A flake-form reinforced W-Fe of the present example3The rapid preparation method of the Al fine-grain heavy tungsten alloy comprises the following steps and process conditions:
(1) the raw material components are proportioned as follows: with W, Fe3Al powder is used as alloy raw material, and the raw materials comprise W85% and Fe according to the following mass percentage315 percent of Al. Purity of W powder>99.9％，Fe3Purity of Al powder>99％。
(2) Mixing the W powder and Ni3And (3) putting the Al powder into different ball milling tanks, performing two-step ball milling on the Al powder respectively on a stirring ball mill, and then performing low-energy ball milling on the Al powder to uniformly mix the Al powder. The two-step ball milling process comprises the following steps of firstly, feeding at the rotating speed of 180r/minThe low-speed ball milling is carried out for 15h, and then the high-speed ball milling is carried out for 9h at 320 r/min. To obtain a fine composite powder containing a flaky intermetallic compound powder and uniformly mixed.
(3) And carrying out in-situ oxidation treatment on the uniformly mixed composite powder at room temperature for 8 days.
(4) The powder after the in-situ oxidation is filled into a graphite die and then is placed in a heating cavity of a spark plasma sintering system, the spark plasma two-step sintering is carried out after the vacuum pumping, and the sintering process conditions are as follows: the sintering vacuum degree is less than 3Pa, the sintering temperature is 1250 ℃, the sintering pressure is 60MPa, the heating rate is 150 ℃/min, and the heat preservation time is 10 min. The second step is that: the sintering vacuum degree is less than 3Pa, the sintering temperature is 1400 ℃, the sintering pressure is 50MPa, the heating rate is 300 ℃/min, and the heat preservation time is 0 min.
By the preparation method, W-Fe with uniform tissue is obtained3The Al alloy has crystal grain less than 2 micron, relative density greater than 99%, macro hardness 74.6HRA and bending strength 835 MPa.
Example 4
A sheet-like reinforced W-Ti of the present example3The rapid preparation method of the Al fine-grain heavy tungsten alloy comprises the following steps and process conditions:
(1) the raw material components are proportioned as follows: with W, Ti3Al powder is used as an alloy raw material, and W93 percent and Ti are mixed according to the following mass percentage37 percent of Al. Purity of W powder>99.9％，Ti3Purity of Al powder>99％。
(2) Mixing the W powder and Ni3And putting the Al powder into a ball milling tank, and carrying out one-step ball milling and mixing on a planetary ball mill. The one-step ball milling process is ball milling for 17 hours at the rotating speed of 450 r/min. To obtain a fine composite powder containing a flaky intermetallic compound powder and uniformly mixed.
(3) And carrying out in-situ oxidation treatment on the uniformly mixed composite powder for 5 days at room temperature.
(4) The powder after the in-situ oxidation is filled into a graphite die and then is placed in a heating cavity of a spark plasma sintering system, the spark plasma two-step sintering is carried out after the vacuum pumping, and the sintering process conditions are as follows: the sintering vacuum degree is less than 3Pa, the sintering temperature is 1220 ℃, the sintering pressure is 70MPa, the heating rate is 170 ℃/min, and the heat preservation time is 5 min. The second step is that: the sintering vacuum degree is less than 3Pa, the sintering temperature is 1350 ℃, the sintering pressure is 60MPa, the heating rate is 250 ℃/min, and the heat preservation time is 0 min.
By the preparation method, W-Ti with uniform tissue is obtained3The Al alloy has crystal grain less than 2 micron, relative density greater than 99%, macro hardness of 82.5HRA and bending strength of 415 MPa.
Comparative example
W-Ni of this comparative example3The traditional liquid phase preparation method of the Al alloy comprises the following steps and process conditions:
(1) the raw material components are proportioned as follows: with W, Ni3Al powder is used as an alloy raw material, and W94 percent and Ni are mixed according to the following mass percentage36 percent of Al. Purity of W powder>99.9％，Ni3Purity of Al powder>99％。
(2) Mixing the W powder and Ni3And (3) putting the Al powder into a ball milling tank, and carrying out one-step high-energy ball milling on the raw material mixed powder on a planetary ball mill. The one-step ball milling process is ball milling for 17 hours at the rotating speed of 450 r/min.
(3) After the uniformly mixed raw material powder is loaded into a die and pressed, placing a sample into a heating cavity of a vacuum sintering furnace for traditional liquid phase sintering, wherein the sintering process conditions are as follows: the heating rate is 5 ℃/min, the sintering temperature is 1450 ℃, and the heat preservation time is 120 min.
By the preparation method, W-Ni with uniform tissue is obtained3The Al alloy has crystal grain of greater than 10 micron, relative density less than 95%, macro hardness of 61.1HRA and bending strength of 350 MPa.
As can be seen from the examples 1 and 2 and the comparative example, the conventional liquid phase sintering has a low temperature rise rate and a long temperature rise and preservation time, so that the crystal grains are easily grown, the fine grain strengthening effect is further influenced, and the mechanical property of the alloy is reduced. More importantly, compared with the traditional tungsten alloy microstructure, the novel flaky binding phase and the in-situ authigenic nano-alumina particle microstructure can greatly improve the mechanical properties such as the bending strength and the like of the alloy due to the synergistic enhancement effect.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (8)
1. A preparation method of a flaky intermetallic compound reinforced fine-grained tungsten alloy is characterized by comprising the following preparation steps:
(1) mixing raw material tungsten powder and intermetallic compound powder according to a certain mass percentage; the intermetallic compound is Ni3Al、Fe3Al、Ti3At least one of Al;
(2) carrying out high-energy ball milling on the prepared raw material powder in a ball mill to obtain fine composite powder which contains flaky intermetallic compound powder and is uniformly mixed;
(3) carrying out in-situ oxidation treatment on the composite powder obtained in the step (2), and carrying out in-situ self-generation of nano alumina particles on the surface of the flaky intermetallic compound powder;
(4) and (4) performing discharge plasma sintering on the composite powder obtained in the step (3) to obtain the flaky intermetallic compound reinforced fine-grained tungsten alloy.
2. The method of preparing a platelet intermetallic compound reinforced fine grain tungsten alloy as claimed in claim 1, wherein: in the step (1), the tungsten powder and intermetallic compound powder are prepared by the following materials in percentage by mass: 85-95% of tungsten powder and 5-15% of intermetallic compound powder.
3. The method of preparing a platelet intermetallic compound reinforced fine grain tungsten alloy as claimed in claim 1, wherein: and (3) performing high-energy ball milling in the step (2) in a stirring type ball milling mode, a vibration type ball milling mode or a planetary type ball milling mode.
4. The method of preparing a platelet intermetallic compound reinforced fine grain tungsten alloy as claimed in claim 1, wherein: the high-energy ball milling in the step (2) comprises a ball milling method or a separate ball milling method; the ball milling method is to perform high-energy ball milling on the mixed powder of the tungsten powder and the intermetallic compound raw material together, and the ball milling method is to perform high-energy ball milling on the tungsten powder and the intermetallic compound powder respectively and then uniformly mix the two high-energy ball milling raw material powders through low-energy ball milling.
5. The method of preparing a platelet intermetallic compound reinforced fine grain tungsten alloy as claimed in claim 1, wherein: the high-energy ball milling in the step (2) comprises one-step ball milling or two-step ball milling; the first-step ball milling is ball milling for 0-24 hours at a rotating speed of less than 1000r/min, and the second-step ball milling is ball milling at a low speed of less than 300r/min for 0-20 hours and then ball milling at a high speed of more than 300r/min for 0-4 hours.
6. The method of preparing a platelet intermetallic compound reinforced fine grain tungsten alloy as claimed in claim 1, wherein: the in-situ oxidation treatment in the step (3) comprises room-temperature in-situ oxidation or low-temperature heat treatment in-situ oxidation; wherein the room-temperature in-situ oxidation time is 0-10 days; the temperature of the low-temperature heat treatment in-situ oxidation is 50-300 ℃, and the oxidation time is 0-24 h.
7. The method of preparing a platelet intermetallic compound reinforced fine grain tungsten alloy as claimed in claim 1, wherein: the spark plasma sintering in the step (4) comprises a one-step sintering method or a two-step sintering method;
the process conditions of the one-step sintering method are as follows:
the sintering vacuum degree is less than 3Pa, the sintering temperature is 1350-1500 ℃, the sintering pressure is 30-100 MPa, the heating rate is 100-400 ℃/min, and the heat preservation time is 0-30 min;
the two-step sintering method comprises the following process conditions:
the first step is as follows: the sintering vacuum degree is less than 3Pa, the sintering temperature is 1000-1250 ℃, the sintering pressure is 30-100 MPa, the heating rate is 50-400 ℃/min, and the heat preservation time is 3-20 min;
the second step is that: the sintering vacuum degree is less than 3Pa, the sintering temperature is 1300-1400 ℃, the sintering pressure is 30-100 MPa, the heating rate is 200-400 ℃/min, and the heat preservation time is 0 min.
8. A flaky intermetallic compound reinforced fine-grained tungsten alloy is characterized in that: prepared by the method of any one of claims 1 to 7.
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