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CN111636026A - High-niobium low-density refractory multi-principal-element alloy and vacuum drop casting method thereof - Google Patents

High-niobium low-density refractory multi-principal-element alloy and vacuum drop casting method thereof Download PDF

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CN111636026A
CN111636026A CN202010529714.7A CN202010529714A CN111636026A CN 111636026 A CN111636026 A CN 111636026A CN 202010529714 A CN202010529714 A CN 202010529714A CN 111636026 A CN111636026 A CN 111636026A
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niobium
alloy
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drop casting
titanium
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CN111636026B (en
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刘鑫旺
白朱成
姚俊卿
蒋文明
樊自田
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Huazhong University of Science and Technology
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    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C30/00Alloys containing less than 50% by weight of each constituent
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22DCASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/02Making non-ferrous alloys by melting
    • C22C1/03Making non-ferrous alloys by melting using master alloys

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Abstract

The invention belongs to the technical field of metal materials and discloses a high-niobium low-density refractory multi-principal-element alloy and a vacuum drop casting method thereof, wherein the multi-principal-element alloy comprises the following components in percentage by atom (35-45): (18.33-21.67): (18.33-21.67): (18.33-21.67), and the phase structure of the multi-principal-element alloy is a single BCC structure. Among the constituent elements of the multi-principal-element alloy, niobium is a main refractory element and plays a main role, the high niobium content enables the alloy to have the characteristics of high refractoriness and high toughness, the moderate aluminum content is favorable for keeping good oxidation resistance and low density, and the moderate titanium content is favorable for keeping good oxidation resistance and certain toughness; and a drop casting method is adopted, so that the defect that a small cast ingot with a certain size is difficult to prepare due to high viscosity of refractory multi-principal-element alloy in the traditional suction casting technology is effectively overcome.

Description

High-niobium low-density refractory multi-principal-element alloy and vacuum drop casting method thereof
Technical Field
The invention belongs to the technical field of metal materials, and particularly relates to a high-niobium low-density refractory multi-principal-element alloy and a vacuum drop casting method thereof.
Background
The multi-principal-element alloy is a novel alloy design concept proposed in recent years, the concept expands the component range of the traditional alloy, greatly enriches the types of alloy materials, and generally requires that the mole percentage of each element in the alloy is more than 5%.
The research of researchers on the multi-principal-element alloy shows that the multi-principal-element alloy has many kinds of metal elements and large element disorder degree, so that the solidified alloy does not form a large amount of intermetallic compounds like the traditional alloy but promotes the mixing among elements, so that the multi-principal-element alloy forms a simple phase structure, such as a single-phase body-centered cubic phase or a face-centered cubic phase, and simultaneously inhibits the formation of brittle intermetallic compounds. The characteristic of easy formation of single solid solution enables the multi-principal element alloy to show excellent properties, such as (1) high hardness; (2) good corrosion resistance; (3) good wear resistance; (4) good high temperature resistance; (5) high work hardening capacity.
In order to fully exert the high-temperature performance advantages of the multi-principal-element alloy to meet the development requirements of the high-temperature alloy, researchers begin to turn their attention to refractory multi-principal-element alloys. The refractory multi-principal element alloy is prepared by adopting refractory metal elements, such as elements of a IV main group (Ti, Zr, Hf), a V main group (V, Nb, Ta) and a VI main group (Cr, Mo, W), adjusting the element proportion and utilizing a multi-principal element alloying method. The refractory multi-principal-element alloy often has high-temperature stability, and is expected to be applied to the high-temperature fields of aerospace, power generation industry and the like so as to make up for the defects caused by the fact that the use temperature of the traditional high-temperature alloy reaches the theoretical limit. However, the refractory multi-element alloy has the disadvantages of high temperature performance, and mainly comprises the following four points:
one is poor room temperature plasticity. Most refractory multi-principal element alloys have a room temperature compressive plastic strain of less than 5%, and only part of the refractory multi-principal element alloys have a certain room temperature compressive plastic property.
The second is that the density tends to be greater. The density of part of refractory multi-principal element alloy is more than 10g/cm3(e.g., VNbTaMoW), it is difficult to meet the requirement of light weight in the use of the alloy.
Thirdly, the oxidation resistance is poor. Partially refractory multi-principal element alloys with high plasticity tend to contain very high contents of active elements such as Ti, Zr, Hf and the like, such as typical Ti1.5ZrHf0.5Nb0.5Ta0.5In which Ti content is as high as 37.5% and Zr content is as high as 25%, resulting in poor oxidation resistance.
Fourthly, the preparation difficulty of the small-sized cast ingot is high. For example, in the case of arc melting, the refractory multi-element alloy often contains both refractory elements with a very high melting point and low-boiling-point elements (such as aluminum), and high-temperature melting causes the low-boiling-point elements to be violently volatilized. And the refractory multi-principal-element alloy has higher viscosity, and the ingot with a certain size is difficult to prepare by adopting the traditional suction casting technology.
Therefore, the refractory multi-principal-element alloy and the casting method thereof need to be explored and improved more deeply, so that a high-purity small-sized ingot and a high-purity small-sized ingot casting process are obtained, and popularization and application are realized.
Disclosure of Invention
Aiming at the defects or improvement requirements of the prior art, the invention provides a high-niobium low-density refractory multi-principal-element alloy and a vacuum drop casting method thereof, aiming at solving the problems of high density, poor room-temperature shaping and high preparation difficulty of small ingots (or castings) of the existing refractory multi-principal-element alloy, the invention adopts a method of firstly preparing a titanium-aluminum intermediate alloy and then mixing and smelting the intermediate alloy and other elements, so that the violent volatilization of aluminum in the smelting process caused by the fact that the boiling point (2327 ℃) of the aluminum is lower than the melting point (2750 ℃) of the niobium can be effectively avoided, and the accuracy of components is ensured; meanwhile, a drop casting method is adopted, the defect that a small ingot with a certain size is difficult to prepare due to high viscosity of refractory multi-principal-element alloy in the traditional suction casting technology is effectively overcome, and high-purity small ingots (castings) with various sizes and specifications can be quickly prepared.
To achieve the above object, according to one aspect of the present invention, there is provided a high-niobium low-density refractory multi-element alloy, the multi-element alloy comprising niobium, aluminum, titanium and vanadium, the ratio of the atoms of niobium, aluminum, titanium and vanadium being (35-45): (18.33-21.67): (18.33-21.67): (18.33-21.67), and the phase structure of the multi-principal-element alloy is a single BCC structure.
Further, the yield strength at room temperature of the multi-principal-element alloy is 1043MPa, and the density of the multi-principal-element alloy is 6.19g/cm3The room temperature specific strength is 167 MPa-cm3/g。
Further, it is preferable that the atomic ratio of niobium, aluminum, titanium, and vanadium is 2: 1: 1: 1.
according to another aspect of the present invention, there is provided a vacuum drop casting method suitable for use with a high niobium low density refractory multi-host alloy as described above, said vacuum drop casting method essentially comprising the steps of:
(1) according to the atomic ratio (35-45): (18.33-21.67): (18.33-21.67): (18.33-21.67) weighing niobium, aluminum, titanium and vanadium respectively;
(2) putting the weighed raw materials into a vacuum electric arc furnace, wherein titanium and aluminum are placed in the same smelting station, and an aluminum block is embedded under titanium particles; placing niobium and vanadium in another smelting station, wherein vanadium is on the lower niobium;
(3) vacuumizing a vacuum arc furnace, and filling argon as a smelting medium;
(4) firstly, melting titanium and aluminum into a titanium-aluminum intermediate alloy, melting niobium and vanadium into a niobium-vanadium intermediate alloy, and then turning the niobium-vanadium intermediate alloy above the titanium-aluminum intermediate alloy by using a mechanical handle to enable the niobium-vanadium intermediate alloy and the titanium-aluminum intermediate alloy to be positioned in the same melting station;
(5) repeatedly smelting for many times, and thoroughly melting each time until niobium, aluminum, titanium and vanadium are completely mixed and dissolved, and cooling to obtain the high-niobium low-density refractory multi-principal-element alloy;
(6) and moving the high-niobium low-density refractory multi-principal-element alloy to a drop casting station, striking an arc and slowly increasing current to gradually melt the high-niobium low-density refractory multi-principal-element alloy, when the alloy at the bottom of the drop casting station is completely melted, quickly dropping most of molten metal into a drop casting mold at the lower part of the drop casting station, quickly increasing the current to quickly and completely melt the residual alloy attached to the inner wall of the drop casting station and flow into the drop casting mold, and cooling to obtain a casting with a required size.
Further, in the step (3), the furnace door is closed, the furnace is vacuumized by using a molecular pump, a certain amount of argon is filled to 0.03MPa, and then the furnace is vacuumized again to 2 × 10 DEG-3Pa, repeating for three times; finally, argon gas was introduced into the furnace to 0.05MPa to serve as a melting medium.
Further, the maximum current for melting is 800A, the maximum current for melting is kept for 90s each time, and an electromagnetic field is adopted to assist in stirring the melt all the time in the melting process.
Further, in the step (4), the smelting station is a water-cooled copper crucible.
Furthermore, the current adopted during drop casting is 900-1000A, and the drop casting mold is a water-cooling copper mold.
Further, the mass of niobium was 42.94g, the mass of aluminum was 6.24g, the mass of titanium was 11.06g, the mass of vanadium was 23.76g, and the total weight was 84 g.
Generally, compared with the prior art, the high-niobium low-density refractory multi-principal-element alloy and the vacuum drop casting method thereof provided by the invention have the following beneficial effects:
1. the ratio of the atoms of niobium, aluminum, titanium and vanadium is (35-45): (18.33-21.67): (18.33-21.67): (18.33-21.67), the multi-principal element alloy has a single BCC structure, niobium is a main refractory element and plays a main role in the composition elements of the multi-principal element alloy, the alloy has the characteristics of refractory property and high toughness due to the high niobium content, the moderate aluminum content is favorable for keeping good oxidation resistance and low density, and the moderate titanium content is favorable for keeping good oxidation resistance and certain toughness.
2. Preferably the niobium, the aluminum, theThe atomic ratio of the titanium to the vanadium is 2: 1: 1: 1, i.e. Nb2The yield strength of the AlTiV at room temperature can reach 1043MPa, and the density is 6.19g/cm3The specific strength at room temperature can reach 167 MPa-cm3(iv)/g, room temperature compressive plastic strain greater than 100%; compared with other existing refractory multi-principal element alloys (such as VNbTaMoW and Ti)1.5ZrHf0.5Nb0.5Ta0.5) The refractory multi-principal element alloy exhibits the characteristics of high room temperature specific strength, low density and high room temperature plasticity.
3. The drop casting method adopts a method of firstly preparing the titanium-aluminum intermediate alloy and then mixing and smelting the intermediate alloy and other elements, so that violent volatilization of aluminum in the smelting process due to the fact that the boiling point (2327 ℃) of the aluminum is lower than the melting point (2750 ℃) of the niobium can be effectively avoided, and the accuracy of components is guaranteed; by adopting the drop casting method, the defect that the traditional suction casting technology is difficult to prepare small ingots with certain sizes due to high viscosity of refractory multi-principal-element alloy is effectively overcome, and the high-purity small ingots (castings) with various sizes and specifications can be quickly prepared.
4. The drop casting method has the advantages of accurate components, high purity, high yield, low cost, high efficiency and quick forming of small cast ingots (castings) and the like.
Drawings
FIG. 1 is a gold phase diagram of a high niobium low density refractory multi-host alloy provided by the present invention;
FIG. 2 is an X-ray diffraction (XRD) pattern of the high niobium low density refractory multi-element alloy of FIG. 1;
fig. 3 is a stress-strain plot of the high niobium low density refractory multi-host alloy of fig. 1 after room temperature compression.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Referring to fig. 1, fig. 2 and fig. 3, the present invention provides a high-niobium low-density refractory multi-element alloy, the multi-element alloy comprises niobium, aluminum, titanium and vanadium, and the atomic ratio of niobium, aluminum, titanium and vanadium is (35-45): (18.33-21.67): (18.33-21.67): (18.33 to 21.67), preferably 2: 1: 1: 1, and the phase structure of the multi-principal element alloy is a single BCC structure.
The invention also provides a vacuum drop casting method suitable for the high-niobium low-density refractory multi-principal-element alloy, which mainly comprises the following steps:
step one, according to the atomic ratio of (35-45): (18.33-21.67): (18.33-21.67): (18.33-21.67) weighing niobium, aluminum, titanium and vanadium respectively.
Specifically, the alloy composition is designed to be Nb2And AlTiV, polishing the raw materials, removing surface impurities, ultrasonically cleaning in absolute ethyl alcohol, drying, and accurately weighing the four raw materials of niobium, aluminum, titanium and vanadium by using a micrometer electronic balance.
In one embodiment, 42.94g niobium, 6.24g aluminum, 11.06g titanium, 23.76g vanadium, and 84g total weight; the raw material purity of each component of the alloy is more than 99.9%. Preferably, the ratio of the atoms of niobium, aluminum, titanium and vanadium is 2: 1: 1: 1.
placing the weighed raw materials into a vacuum electric arc furnace, wherein titanium and aluminum are placed in the same smelting station, and an aluminum block is embedded under titanium particles; the niobium and vanadium are placed in another smelting station, and the vanadium is on the lower niobium.
Specifically, the raw materials weighed in the step one are placed into a high vacuum arc furnace, titanium and aluminum are placed in the same smelting station (aluminum blocks are embedded under titanium grains) according to the principle that elements with low melting points are placed below and elements with high melting points are placed above, and niobium and vanadium are placed in the other smelting station (vanadium is placed below and niobium is placed above).
And step three, after the vacuum arc furnace is vacuumized, filling argon as a smelting medium.
Specifically, the furnace door is closed, and the furnace is pumped out by using a molecular pumpVacuum, filling a certain amount of high-purity argon to about 0.03MPa, and then re-vacuumizing to 2 × 10-3Pa, repeating for three times, reducing the air content in the furnace to the maximum extent, creating a high-purity casting environment, and finally filling high-purity argon into the furnace to about 0.05MPa to serve as a smelting medium.
And step four, firstly melting titanium and aluminum into a titanium-aluminum intermediate alloy, melting niobium and vanadium into a niobium-vanadium intermediate alloy, and then turning the niobium-vanadium intermediate alloy above the titanium-aluminum intermediate alloy by using a mechanical handle to enable the titanium-aluminum intermediate alloy and the niobium-vanadium intermediate alloy to be positioned in the same melting station.
Specifically, titanium and aluminum are firstly melted into a titanium-aluminum intermediate alloy, niobium and vanadium are melted into a niobium-vanadium intermediate alloy, and then the niobium-vanadium intermediate alloy is turned over the titanium-aluminum intermediate alloy by a mechanical handle so that the titanium-aluminum intermediate alloy and the niobium-vanadium intermediate alloy are positioned in the same melting station.
In the embodiment, the smelting station is a water-cooled copper crucible, the maximum smelting current is 800A, the maximum current is kept for smelting for 90s in each smelting, and an electromagnetic field is adopted to assist in stirring the melt all the time in the smelting process.
And step five, repeatedly smelting for many times, and completely melting each time until niobium, aluminum, titanium and vanadium are completely mixed and dissolved, and cooling to the high-niobium low-density refractory multi-principal-element alloy.
Specifically, the maximum current of each melting is 800A, the maximum current melting time is kept to be 90s, the melting is repeated for six times, each melting is conducted until the four elements are completely mixed, and the alloy ingot is obtained after cooling.
And sixthly, moving the high-niobium low-density refractory multi-principal-element alloy into a drop casting station, striking an arc and slowly increasing current to gradually melt the high-niobium low-density refractory multi-principal-element alloy, when the alloy at the bottom of the drop casting station is completely melted, quickly dropping most of metal liquid into a drop casting mold at the lower part of the drop casting station, quickly increasing the current to quickly and completely melt the residual alloy attached to the inner wall of the drop casting station and flow into the drop casting mold, and cooling to obtain a casting with a required size.
Specifically, an alloy ingot is moved to a drop casting station by a manipulator, the alloy ingot is gradually melted by striking an arc and slowly increasing current, when the alloy at the bottom of the drop casting station is completely melted, most of molten metal is quickly dropped into a drop casting mold at the lower part of the drop casting station, the current is quickly increased to 900-1000A, so that the residual alloy attached to the inner wall of the drop casting station is quickly and completely melted and flows into the drop casting mold, and a high-purity small ingot with the size of about 10mm multiplied by 20mm multiplied by 70mm is obtained after cooling. The maximum current of the drop casting is 1000A, the drop casting mold is a water-cooling copper mold, and grooves with various dimensions are formed in the drop casting mold, so that high-purity small ingots (castings) with various dimensions can be rapidly prepared according to actual needs.
The high niobium, low density refractory multi-element alloy (i.e., as-cast Nb) produced in this example2AlTiV alloy) were tested as follows:
1. and (3) metallographic microstructure observation: obvious grain boundaries can be observed in the alloy, coarse grains have a dendritic form inside, and the structure is very dense, as shown in figure 1.
2. Phase analysis: indicating that the alloy phase structure is a single BCC structure, as shown in FIG. 2.
3. Density was measured using archimedes drainage method: the alloy density was measured to be about 6.19 g.cm-3
4. Room temperature compression test: the yield strength of the alloy at room temperature can reach 1043MPa, and the compression plastic strain at room temperature exceeds 100 percent, as shown in figure 3. In addition, the alloy has a low density of about 6.19g/cm3The specific strength at room temperature can reach 167 MPa-cm3/g。
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (9)

1. A high-niobium low-density refractory multi-principal-element alloy is characterized in that:
the multi-principal-element alloy comprises the following components of niobium, aluminum, titanium and vanadium, wherein the atomic ratio of niobium to aluminum to titanium to vanadium is (35-45): (18.33-21.67): (18.33-21.67): (18.33-21.67), and the phase structure of the multi-principal-element alloy is a single BCC structure.
2. The high niobium low density refractory multi-host alloy of claim 1, wherein: the room-temperature yield strength of the multi-principal-element alloy is 1043MPa, and the density of the multi-principal-element alloy is 6.19g/cm3The room temperature specific strength is 167 MPa-cm3/g。
3. The high niobium low density refractory multi-host alloy of claim 1, wherein: the ratio of the atoms of niobium, aluminum, titanium and vanadium is 2: 1: 1: 1.
4. a vacuum drop casting method suitable for use with the high niobium low density refractory multi-element alloy of any one of claims 1 to 3, wherein said vacuum drop casting method comprises the steps of:
(1) according to the atomic ratio (35-45): (18.33-21.67): (18.33-21.67): (18.33-21.67) weighing niobium, aluminum, titanium and vanadium respectively;
(2) putting the weighed raw materials into a vacuum electric arc furnace, wherein titanium and aluminum are placed in the same smelting station, and an aluminum block is embedded under titanium particles; placing niobium and vanadium in another smelting station, wherein vanadium is on the lower niobium;
(3) vacuumizing a vacuum arc furnace, and filling argon as a smelting medium;
(4) firstly, melting titanium and aluminum into a titanium-aluminum intermediate alloy, melting niobium and vanadium into a niobium-vanadium intermediate alloy, and then turning the niobium-vanadium intermediate alloy above the titanium-aluminum intermediate alloy by using a mechanical handle to enable the niobium-vanadium intermediate alloy and the titanium-aluminum intermediate alloy to be positioned in the same melting station;
(5) repeatedly smelting for many times, and thoroughly melting each time until niobium, aluminum, titanium and vanadium are completely mixed and dissolved, and cooling to obtain the high-niobium low-density refractory multi-principal-element alloy;
(6) and moving the high-niobium low-density refractory multi-principal-element alloy to a drop casting station, striking an arc and slowly increasing current to gradually melt the high-niobium low-density refractory multi-principal-element alloy, when the alloy at the bottom of the drop casting station is completely melted, quickly dropping most of molten metal into a drop casting mold at the lower part of the drop casting station, quickly increasing the current to quickly and completely melt the residual alloy attached to the inner wall of the drop casting station and flow into the drop casting mold, and cooling to obtain a casting with a required size.
5. The vacuum drop casting method for high-niobium low-density refractory multi-principal-element alloy according to claim 4, wherein in the step (3), the furnace door is closed, the furnace is vacuumized by using a molecular pump, a certain amount of argon is filled to 0.03MPa, and then the furnace is vacuumized again to 2 × 10-3Pa, repeating for three times; finally, argon gas was introduced into the furnace to 0.05MPa to serve as a melting medium.
6. The vacuum drop casting method for a high niobium low density refractory multi-host alloy as claimed in claim 4 wherein: the maximum current for melting is 800A, the maximum current for melting is kept for 90s each time, and an electromagnetic field is adopted to assist in stirring the melt all the time in the melting process.
7. The vacuum drop casting method for a high niobium low density refractory multi-host alloy as claimed in claim 4 wherein: in the step (4), the smelting station is a water-cooled copper crucible.
8. The vacuum drop casting method for a high niobium low density refractory multi-host alloy as claimed in claim 4 wherein: the current adopted during drop casting is 900-1000A, and the drop casting mold is a water-cooling copper mold.
9. The vacuum drop casting method for a high niobium low density refractory multi-host alloy as claimed in claim 4 wherein: the mass of niobium was 42.94g, the mass of aluminum was 6.24g, the mass of titanium was 11.06g, the mass of vanadium was 23.76g, and the total weight was 84 g.
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CN116065076A (en) * 2021-11-04 2023-05-05 哈尔滨工业大学 Low-density refractory multi-principal element alloy and preparation method and application thereof

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