CN113462994B - Vacuum melting process for removing matrix oxide impurities in Zr-based amorphous alloy - Google Patents
Vacuum melting process for removing matrix oxide impurities in Zr-based amorphous alloy Download PDFInfo
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- CN113462994B CN113462994B CN202110630896.1A CN202110630896A CN113462994B CN 113462994 B CN113462994 B CN 113462994B CN 202110630896 A CN202110630896 A CN 202110630896A CN 113462994 B CN113462994 B CN 113462994B
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
- C22C45/10—Amorphous alloys with molybdenum, tungsten, niobium, tantalum, titanium, or zirconium or Hf as the major constituent
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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
- C22C1/11—Making amorphous alloys
Abstract
The invention discloses a vacuum melting process for removing matrix oxide impurities in Zr-based amorphous alloy, which comprises the following steps: carrying out vacuum melting on the Zr-based amorphous alloy in a furnace; step two: flushing inert gas into the furnace; step three: feeding a calcium wire into the melt; step four: stirring the melt to cause the calcium and the impurities of the matrix oxide to carry out redox reaction to form CaO; step five: standing for a certain time, and removing the CaO after the CaO floats upwards. The method is simple and convenient to operate, matrix oxide impurities in the Zr-based amorphous alloy are reduced by using calcium element to form oxide CaO, the CaO is layered with the Zr-based amorphous alloy melt after the CaO floats upwards by using the characteristics of small density and easy floating of the CaO and standing for a certain time, the matrix oxide impurities in the Zr-based amorphous alloy are finally removed, and the purity of the Zr-based amorphous alloy is improved.
Description
Technical Field
The invention belongs to the technical field of amorphous alloys, and particularly relates to a vacuum melting process for removing matrix oxide impurities in a Zr-based amorphous alloy.
Background
Zr in the Zr-based amorphous alloy is easy to combine with oxygen, so the Zr needs to be smelted in a vacuum environment, but certain oxygen content is difficult to avoid in raw materials and a smelting furnace, and ZrO can be formed by reaction in the smelting process2And the like, and the presence of the matrix oxide impurities can adversely affect the material properties and surface quality of the amorphous material. In the smelting of Zr-based amorphous alloy, because ZrO2The density of matrix oxide impurities is close to that of amorphous alloy, and the impurities are not easy to float upwards and remove, so that the amorphous alloy can usually utilize elements such as rare earth and the like to remove oxygen, form rare earth oxide impurities and then remove the impurities, but the cost of the rare earth alloy is higher, meanwhile, the content of the rare earth alloy cannot be adjusted in real time according to the oxygen content in a smelting sample, the actual deoxidation demand cannot be accurately calculated, and the method is not beneficial to popularization and application in the Zr-based amorphous alloy smelting process.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art.
Therefore, the invention provides a vacuum melting process for removing matrix oxide impurities in Zr-based amorphous alloy, and the vacuum melting process for removing the matrix oxide impurities in the Zr-based amorphous alloyThe process utilizes calcium element and ZrO2And the formed CaO oxide is effectively removed by oxidation-reduction reaction of the impurities of the matrix oxide.
The vacuum melting process for removing Zr-based oxide impurities in the Zr-based amorphous alloy comprises the following steps: carrying out vacuum melting on the Zr-based amorphous alloy in a furnace; step two: flushing inert gas into the furnace; step three: feeding a calcium wire into the melt; step four: stirring the melt to cause the calcium and the impurities of the matrix oxide to carry out redox reaction to form CaO; step five: standing for a certain time, and removing the CaO after the CaO floats upwards.
According to an embodiment of the invention, in the first step, the Zr-based amorphous alloy is added into the crucible, the crucible is placed in a vacuum induction furnace, then the crucible is heated to 950-1300 ℃ for smelting, and after the melting is finished, a sample is taken to detect the actual oxygen content of the melt.
According to an embodiment of the present invention, in the second step, argon gas is flushed into the furnace to increase the vacuum pressure to 200-500 pa.
According to one embodiment of the invention, a wire feeding mechanism is arranged on a furnace cover of the vacuum induction furnace, and the calcium wire is hermetically fed into the crucible through the wire feeding mechanism.
According to one embodiment of the invention, the feeding amount of the calcium line in the third step meets the following formula:
W1＝40*(W2*(O1-O2))/(16*δ)
wherein, W1Represents the feeding amount of the calcium line; w2Represents the total amount of the Zr-based amorphous alloy melted; o is1Represents the actual oxygen content; o is2Represents a target oxygen content; δ represents the yield of pure calcium line.
According to one embodiment of the invention, the diameter of the calcium wire is 5-50 mm.
According to one embodiment of the invention, the feeding speed of the calcium wire is 0.05-1 m/s.
According to one embodiment of the invention, the total feed time of the calcium wire is 20 to 60 s.
According to an embodiment of the invention, in the fourth step, the power of the vacuum induction furnace is increased by 5% -20% to perform electromagnetic induction stirring.
According to an embodiment of the invention, the standing time in the fifth step is 5-20 minutes.
The method has the beneficial effects that the method is simple and convenient to operate, matrix oxide impurities in the Zr-based amorphous alloy are reduced by using calcium element to form oxide CaO, the characteristics of small density and easiness in floating of CaO are utilized, and the CaO and the Zr-based amorphous alloy melt are layered after the CaO floats upwards by standing for a certain time, so that the matrix oxide impurities in the Zr-based amorphous alloy are removed finally, and the purity of the Zr-based amorphous alloy is improved.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims hereof.
In order to make the aforementioned and other objects, features and advantages of the invention more comprehensible, preferred embodiments accompanied with figures are described in detail below.
Detailed Description
The following detailed description of embodiments of the invention is intended to be illustrative, and is not to be construed as limiting the invention.
The following describes a vacuum melting process for removing matrix oxide impurities in a Zr-based amorphous alloy according to an embodiment of the present invention.
The vacuum melting process for removing the matrix oxide impurities in the Zr-based amorphous alloy comprises the following steps: carrying out vacuum melting on the Zr-based amorphous alloy in a furnace; step two: flushing inert gas into the furnace; step three: feeding a calcium wire into the melt; step four: stirring the melt to cause the calcium and the impurities of the matrix oxide to carry out redox reaction to form CaO; step five: standing for a certain time, and removing the CaO after the CaO floats upwards. In the Zr-based amorphous alloy, the matrix oxide impurities are mainly ZrO2。
The method is simple and convenient to operate, matrix oxide impurities in the Zr-based amorphous alloy are reduced by using calcium element to form oxide CaO, the CaO is layered with the Zr-based amorphous alloy melt after the CaO floats upwards by using the characteristics of small density and easy floating of the CaO and standing for a certain time, the matrix oxide impurities in the Zr-based amorphous alloy are finally removed, and the purity of the Zr-based amorphous alloy is improved.
Since calcium (melting point 839 ℃, boiling point 1484 ℃, density 1.55 g/cm)3) Is easy to be gasified in a high-temperature vacuum environment, and the Zr-based amorphous alloy needs to be smelted in the high-temperature vacuum environment, so that calcium can be used in the smelting process of the Zr-based amorphous alloy to remove ZrO2Impurities, the invention further optimizes the smelting process.
Preferably, in the step one, the Zr-based amorphous alloy is added into the crucible, and the crucible is placed in a vacuum induction furnace for smelting, wherein the smelting temperature is 950-. The smelting temperature lower than the boiling point of calcium is set to avoid the gasification of calcium.
More preferably, in the second step, argon gas is flushed into the furnace to increase the vacuum pressure to 200-500 pa. A certain vacuum pressure value is increased by flushing argon, so that the calcium is further prevented from being gasified, and meanwhile, the argon is inert gas, so that the smelting process of the Zr-based amorphous alloy is not influenced.
Further, the feeding amount of the calcium wire in the third step meets the following formula:
W1＝40*(W2*(O1-O2))/(16*δ)
wherein, W1Represents the feeding amount of the calcium line; w2Represents the total amount of the Zr-based amorphous alloy melted; o is1Represents the actual oxygen content; o is2Represents a target oxygen content; δ represents the yield of pure calcium line. That is to say, the feeding amount of the calcium wire is accurately calculated by a formula, and the adding amount of calcium is accurately controlled, so that the defect that the real-time adjustment cannot be carried out according to the actual oxygen content when the rare earth element is deoxidized is avoided; on the other hand, the calcium is not wasted in utilization, impurities are not generated, and meanwhile, compared with rare earth elements, the cost is greatly reduced.
According to one embodiment of the invention, the furnace cover of the vacuum induction furnace is provided with the wire feeding mechanism, the calcium wire is fed into the crucible in a sealing manner through the wire feeding mechanism, the sealing in the furnace is ensured when the calcium wire is fed, and the smelting effect is improved.
In some embodiments of the invention, the calcium wire has a diameter of 5 to 50 mm. The reasonable diameter of the calcium wire is set, so that on one hand, the feeding amount is conveniently and accurately controlled, and simultaneously, the calcium is conveniently and quickly melted in the Zr-based amorphous alloy melt.
On the basis, the feeding speed of the calcium wire is 0.05-1m/s, and the total feeding time of the calcium wire is 20-60 s.
According to one embodiment of the invention, the power of the vacuum induction furnace is increased by 5% -20% in the fourth step, so as to carry out electromagnetic induction stirring. The power of the vacuum induction furnace is increased to effectively improve the ZrO of the Zr-based amorphous alloy by calcium element2The reduction rate of the impurities.
According to one embodiment of the invention, the standing time in the fifth step is 5-20 minutes. The floating of CaO can be realized after standing, so that the CaO and the Zr-based amorphous alloy melt are layered, and the CaO is convenient to remove.
Example 1
80kg of Zr-based amorphous alloy is smelted in a vacuum induction furnace, after the Zr-based amorphous alloy is smelted, the detected actual oxygen content is 1531ppm, the vacuum degree is increased to 500pa by filling argon, then a pure calcium wire with the diameter of 12mm is fed at the speed of 0.1m/s for 1.8m, the power of the vacuum induction furnace is increased by 10 percent, then the Zr-based amorphous alloy is stood for 10 minutes, and finally the oxygen content in the product is detected to be 452 ppm.
Example 2
30kg of Zr-based amorphous alloy was melted in a vacuum induction furnace, and after melting, the actual oxygen content was measured to be 2000ppm, the target oxygen content was 200ppm, the calcium yield was 90%, and the weight of pure calcium wire was required to be 40 × 30 × (0.2% -0.02%)/0.9/16 ═ 0.15kg, and the cost of the treatment by calcium wire feeding in example 2 was 1.5 yuan per kg, calculated as 10 yuan per kg.
Comparative example 1
30kg of Zr-based amorphous alloy was melted in a vacuum induction furnace, after melting, the actual oxygen content detected was 2000ppm, the target oxygen content was 200ppm, rare earth Y was used for treatment, according to the yield of 95%, the weight of rare earth Y was 2 x 30 (0.2% to 0.02%) 89/3/16/0.95 was 0.21kg, and Y rare earth was calculated according to 200 yuan/kg, and the cost for rare earth Y treatment in comparative example 1 was 42 yuan.
As can be seen from the examples 1 and 2, the oxygen content of the Zr-based amorphous alloy is effectively reduced and the generation of matrix oxide impurities is reduced by adding the calcium element; as can be seen from the example 2 and the comparative example 1, compared with the method adopting rare earth elements to remove oxygen and impurities, the method has the advantages that the cost is greatly reduced, and the economic benefit is better.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an illustrative embodiment," "an example," "a specific example," or "some examples" or the like mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
While embodiments of the invention have been shown and described, it will be understood by those of ordinary skill in the art that: various changes, modifications, substitutions and alterations can be made to the embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the claims and their equivalents.
Claims (9)
1. A vacuum melting process for removing matrix oxide impurities in Zr-based amorphous alloy is characterized by comprising the following steps,
the method comprises the following steps: carrying out vacuum melting on the Zr-based amorphous alloy in a furnace;
step two: flushing inert gas into the furnace;
step three: feeding a calcium wire into the melt;
step four: stirring the melt to cause the calcium and the impurities of the matrix oxide to carry out redox reaction to form CaO;
step five: standing for a certain time, and removing CaO after the CaO floats upwards;
the feeding amount of the calcium wire in the third step meets the following formula:
W1＝40*(W2*(O1-O2))/(16*δ)
wherein, W1Represents the feeding amount of the calcium line; w2Represents the total amount of the Zr-based amorphous alloy melted; o is1Represents the actual oxygen content; o is2Represents a target oxygen content; δ represents the yield of pure calcium line.
2. The vacuum melting process for removing matrix oxide impurities in Zr-based amorphous alloy as claimed in claim 1, wherein in the first step, the Zr-based amorphous alloy is added into a crucible, the crucible is placed in a vacuum induction furnace, then the crucible is heated to 950 ℃ and 1300 ℃ for melting, and after melting down, sampling is carried out to detect the actual oxygen content of the melt.
3. The vacuum melting process for removing the matrix oxide impurities in the Zr-based amorphous alloy as recited in claim 2, wherein in said step two, argon gas is flushed into the furnace to increase the vacuum pressure to 200-500 Pa.
4. The vacuum melting process for removing the matrix oxide impurities in the Zr-based amorphous alloy according to claim 3, wherein a furnace cover of the vacuum induction furnace is provided with a wire feeding mechanism, and the calcium wire is hermetically fed into the crucible through the wire feeding mechanism.
5. The vacuum melting process for removing matrix oxide impurities in Zr-based amorphous alloy according to claim 1, wherein the diameter of said calcium wire is 5-50 mm.
6. The vacuum melting process for removing matrix oxide impurities in Zr-based amorphous alloy according to claim 5, wherein the feeding speed of said calcium wire is 0.05-1 m/s.
7. The vacuum melting process for removing matrix oxide impurities in Zr-based amorphous alloy according to claim 6, wherein the total feeding time of said calcium wire is 20-60 s.
8. The vacuum melting process for removing the matrix oxide impurities in the Zr-based amorphous alloy according to claim 1, wherein in the fourth step, the power of the vacuum induction furnace is increased by 5% -20% to perform electromagnetic induction stirring.
9. The vacuum melting process for removing the matrix oxide impurities in the Zr-based amorphous alloy according to claim 1, wherein the standing time in the fifth step is 5-20 minutes.
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