CN117721334B - Preparation method of TiZrNb-series refractory multi-principal element alloy with uniform equiaxed fine grain structure - Google Patents
Preparation method of TiZrNb-series refractory multi-principal element alloy with uniform equiaxed fine grain structure Download PDFInfo
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- 229910001325 element alloy Inorganic materials 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 230000006698 induction Effects 0.000 claims abstract description 183
- 239000000155 melt Substances 0.000 claims abstract description 78
- 238000003723 Smelting Methods 0.000 claims abstract description 60
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 56
- 239000000956 alloy Substances 0.000 claims abstract description 56
- 238000005275 alloying Methods 0.000 claims abstract description 12
- 239000000725 suspension Substances 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims description 94
- 230000000087 stabilizing effect Effects 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 25
- 238000007711 solidification Methods 0.000 claims description 24
- 239000007789 gas Substances 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 11
- 230000001681 protective effect Effects 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910016285 MxNy Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000013078 crystal Substances 0.000 abstract description 13
- 238000005516 engineering process Methods 0.000 abstract description 4
- 208000012868 Overgrowth Diseases 0.000 abstract description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- 238000002844 melting Methods 0.000 description 10
- 230000008018 melting Effects 0.000 description 9
- 229910052786 argon Inorganic materials 0.000 description 8
- 238000012512 characterization method Methods 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 230000008023 solidification Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000005204 segregation Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000005339 levitation Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
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Abstract
The invention relates to a preparation method of a TiZrNb-series refractory multi-principal element alloy with uniform equiaxed fine grain structure, belonging to the technical field of alloys. The double-coil suspension cold crucible smelting technology is adopted for alloying smelting, then the temperature of the melt is reduced to be between liquidus and solidus, the temperature is raised to be slightly higher than the liquidus based on the temperature, then the power of a main induction coil is reduced instantaneously, and the power of an induction coil at the bottom of a crucible is reduced instantaneously after the temperature of the melt at the top is reduced properly, so that the whole alloy is solidified rapidly under the condition of low superheat degree, overgrowth of crystal grains is avoided, a fine initial structure is obtained, and the mechanical property of an ingot is improved.
Description
Technical Field
The invention relates to a preparation method of a TiZrNb-series refractory multi-principal element alloy with uniform equiaxed fine grain structure, belonging to the technical field of alloys.
Background
The multi-principal element alloy is a newly proposed alloy design concept, and greatly widens the component design space of the metal material. The TiZrNb multi-principal element alloy is a typical refractory multi-principal element alloy system, and is formed by combining Ti, zr, nb, hf, ta, al and other additive elements in different proportions, and has the advantages of multiple element types, high melting point and large difference (the melting point of Nb is 2477 ℃ and the melting point of Ti is 1668 ℃), so that the problems of easy component segregation, coarse and uneven structure and the like in alloy smelting are caused, and the preparation and the production of the alloy are severely restricted.
The common arc melting technology for preparing refractory multi-principal element alloy has the problems of small single preparation amount, large melt temperature gradient and the like. The cold crucible suspension smelting technology can be used for preparing the alloy with the level of several kilograms and has the advantages of cleanness, uniform chemical components and the like. Chinese patent application CN115558814A discloses a cold crucible induction smelting method of a multi-element, high-activity and refractory high-entropy alloy, which can prepare the energetic high-entropy alloy with accurate components and no obvious segregation. However, because the volume of the alloy melt is large, the solidification time is long, and the melt contacts with the cold wall of the crucible, the difference of the cold speeds at different positions is large, so that the initial structure of the alloy is coarse, the grain size distribution is uneven, and the as-cast mechanical property is deteriorated.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for producing a TiZrNb-based refractory multi-element alloy having a uniform equiaxed fine grain structure. The method comprises the steps of adopting a double-coil suspension cold crucible smelting technology to carry out alloying smelting, firstly reducing the temperature of a melt to be between a liquidus line and a solidus line, taking the temperature as a reference, then raising the temperature to be slightly higher than the liquidus line, firstly instantaneously reducing the power of a main induction coil, and then instantaneously reducing the power of an induction coil at the bottom of a crucible after the temperature of a melt at the top is properly reduced, so that the whole alloy is quickly solidified under the condition of low superheat degree, overgrowth of crystal grains is avoided, and a fine initial structure is obtained. The method can effectively reduce the temperature difference of different positions of the melt in the crucible, obtain the multi-principal element alloy with uniform structure, accurate components and no obvious segregation, simultaneously reduce the superheat degree of the alloy before solidification, shorten the solidification time of the alloy melt, effectively reduce the grain size of the cast ingot and improve the mechanical property of the as-cast alloy.
In order to achieve the above object, the technical scheme of the present invention is as follows.
A method for preparing a TiZrNb-based refractory multi-principal element alloy having a uniform equiaxed fine grain structure, the method comprising the steps of:
(1) Placing a TiZrNb series refractory multi-element alloy raw material into a water-cooled copper crucible of a vacuum suspension smelting furnace; vacuumizing the vacuum suspension smelting furnace and filling protective gas;
(2) Firstly starting a main induction coil to gradually increase and maintain the power, and then starting an induction coil at the bottom of a crucible to gradually increase and maintain the power for alloying smelting;
(3) After the alloy is melted, reducing the power of the main induction coil and the induction coil at the bottom of the crucible, so that the temperature of the melt is reduced to be between a liquidus line and a solidus line, the melt is in a semi-solidification state, and the melt is stabilized for 1-2 min;
(4) The power of the main induction coil and the power of the induction coil at the bottom of the crucible are increased, so that the temperature of the alloy melt reaches liquidus, after the melt is liquefied again, the power of the main induction coil and the power of the induction coil at the bottom of the crucible are respectively increased by 5-10 kW, and the temperature is stabilized for 1-2 min;
(5) Closing the power of the main induction coil within 5 seconds, maintaining the power of the induction coil at the bottom of the crucible, closing the power of the induction coil at the bottom of the crucible within 5 seconds after the upper part of the melt is solidified, and cooling;
(6) Repeating the steps (2) to (5), and repeatedly smelting for more than three times to obtain a TiZrNb refractory multi-principal-element alloy cast ingot after smelting is finished;
Wherein the chemical formula of the TiZrNb refractory multi-element alloy is Ti aZrbNbcMxNy, M is more than one of Al, cr, mn, fe, cu, ni, mo, W, N is more than one of B, C, N, O, si, a is more than or equal to 10 and less than or equal to 60,5 and less than or equal to b and less than or equal to 60, c is more than or equal to 15 and less than or equal to 75,0 and less than or equal to x and less than or equal to 10, y is more than or equal to 0 and less than or equal to 5, and a+b+c+x+y=100.
Preferably, a is 15-30, b is 5-60, c is 15-75,0-x is 10, y is 0-5, and a+b+c+x+y=100.
Preferably, in step (1), the shielding gas is an inert gas.
Preferably, in the step (2), the power of the main induction coil is started to be 100-120 kW, the main induction coil is stabilized for 2-3 min, the power is increased to be 180-200 kW, the main induction coil is stabilized for 2-3 min, the main induction coil is increased to be 300-400 kW, and the stable heating power is increased to be 3-5 min; starting an induction coil at the bottom of the crucible to 20-30 kW, stabilizing for 2-3 min, improving to 40-50 kW, stabilizing for 2-3 min, improving to 70-80 kW, and stabilizing for 1-2 min.
Preferably, in the step (3), the power of the main induction coil is reduced to 200-250 kW, and the power of the induction coil at the bottom of the crucible is reduced to 50-60 kW.
Preferably, in the step (4), the power of the main induction coil is increased to 250-300 kW, and the power of the induction coil at the bottom of the crucible is increased to 80-100 kW.
Preferably, in the step (6), when the steps (2) to (5) are repeated, starting the power of the main induction coil to 100-120 kW, and stabilizing for 1-2 min; raising the temperature to 300-400 kW, and stabilizing for 3-5 min; starting the power of an induction coil at the bottom of the crucible to 70-80 kW, and stabilizing for 1-2 min; after the alloy is melted, reducing the power of the main induction coil to 200-250 kW, reducing the power of the induction coil at the bottom of the crucible to 50-60 kW, and stabilizing the melt in a semi-solidification state for 1-2 min; the power of the main induction coil is increased to 250-300 kW, the power of the induction coil at the bottom of the crucible is increased to 80-90 kW, after melt is liquefied again, the power of the main induction coil and the power of the induction coil at the bottom of the crucible are respectively increased by 5-10 kW, and the stability is kept for 1-2 min; and closing the power of the main induction coil within 5 seconds, maintaining the power of the induction coil at the bottom of the crucible, closing the power of the induction coil at the bottom of the crucible within 5 seconds after the upper part of the melt is solidified, and cooling.
Preferably, in the step (6), only the step (2) is repeated in the last smelting.
Preferably, in the step (6), the melting is repeated three to four times.
A TiZrNb-based refractory multi-element alloy with uniform equiaxed fine grain structure is prepared by the method.
Advantageous effects
The invention provides a preparation method of a TiZrNb-series refractory multi-principal-element alloy with uniform equiaxed fine-grain structure, which effectively shortens the solidification time of alloy melt and reduces the temperature difference of different positions in a crucible by carrying out matching control on the power of two groups of induction coils, obtains a TiZrNb-series refractory multi-principal-element alloy ingot with uniform structure, fine grains and accurate components without segregation, effectively improves the mechanical property of an as-cast alloy, has simple process and high operation safety, can realize the smelting of high-capacity refractory multi-principal-element alloy, has high production efficiency, and is suitable for industrial production.
The invention provides a preparation method of a TiZrNb refractory multi-principal-element alloy with a uniform equiaxed fine grain structure, which comprises the steps of starting a main induction coil to gradually increase and maintain power, then starting a crucible bottom induction coil to gradually increase and maintain power, so that the lower part of a melt is completely separated from the crucible wall, the rapid loss of heat at the bottom of the melt is avoided, and the distribution of the temperature field of the whole melt is more uniform. Further, after the alloy is melted, the temperature of the melt is reduced to a temperature between the liquidus and solidus by reducing the main induction coil and the induction coil at the bottom of the crucible, and the superheat degree before final solidification is regulated and controlled by taking the temperature as a reference. And by increasing the power of the main induction coil and the induction coil at the bottom of the crucible again, the temperature of the melt is slightly higher than the liquidus line, the superheat degree of the melt before solidification is ensured to be as low as possible, the temperature field is uniform, a large number of crystal nuclei are uniformly generated in the melt, and meanwhile, the solidification time of the melt is shortened, so that a fine, uniform and equiaxial cast structure is formed. Finally, the power of the main induction coil is firstly and instantaneously reduced, and after a certain time interval, the power of the induction coil at the bottom of the crucible is instantaneously reduced, so that the bottom melt is prevented from being quickly cooled after being contacted with the crucible wall, and the tissue uniformity of the ingot from the top to the bottom is ensured.
The invention provides a TiZrNb refractory multi-principal element alloy with uniform equiaxed fine-grain structure, which has uniform components, equiaxed structure, no dendrite, uniform structures at different positions of cast ingot, fine grains, excellent performance and good consistency.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1
A method for preparing a Ti 24Zr46Nb28Al2 refractory multi-element alloy with a uniform equiaxed fine grain structure, comprising the steps of:
(1) Weighing raw materials with total mass of (1500+/-0.1) g according to atomic percent of Ti, zr and Nb, al=24:46:28:2, uniformly placing clean simple substance elements Ti, zr, nb, al into a smelting crucible, wherein low-melting-point simple substance metals are placed at the bottom of the crucible, the simple substance metal with the highest melting point is placed in the middle area of the crucible, and the rest simple substance elements are uniformly placed in the crucible;
(2) Vacuumizing the vacuum suspension cold crucible smelting furnace, and filling high-purity argon as protective gas after the vacuum degree in the furnace body reaches the high vacuum standard. And (3) carrying out alloying smelting by adopting an induction smelting furnace, wherein the protective gas is argon during smelting. The vacuum degree of the smelting chamber is less than or equal to 1 multiplied by 10 -2 Pa.
(3) Starting a main induction coil to perform alloying smelting, gradually increasing power, firstly adding heating power to 120kW, and stabilizing for 3min; secondly, heating power is increased to 200Kw, and the temperature is stabilized for 3min; and finally, heating power is increased to 400kW, and heating power is stabilized for 5min.
(4) Starting an induction coil at the bottom of the crucible, gradually increasing the power, firstly adding heating power to 30kW, and stabilizing for 3min; then heating power is increased to 50kW, and the heating power is stabilized for 3min; and finally, heating power is increased to 80kW, the temperature is stabilized for 2 minutes, and the alloy melt is completely separated from the crucible wall.
(5) After the alloy is melted, the power of the main induction coil is reduced to 250kW, the power of the induction coil at the bottom of the crucible is reduced to 70kW, the temperature of the melt is reduced to below the liquidus line, the melt is in a semi-solidification state, and the melt is stabilized for 2min.
(6) The power of the main induction coil is added to 300kW, the power of the induction coil at the bottom of the crucible is added to 100kW, the temperature of the melt reaches liquidus, and after the melt is liquefied again, the heating power is increased by 10kW again, and the temperature is stabilized for 2min.
(7) And firstly, reducing the power of the main induction coil to the minimum in three seconds, and after the upper part of the melt is solidified, reducing the power of the induction coil at the bottom of the crucible to the minimum in three seconds, and then, turning off a heating power supply to obtain the alloy ingot cooled to the room temperature.
(8) And (5) heating and smelting the cast ingot again. Firstly, heating power of a main induction coil is added to 120kW, and the main induction coil is stabilized for 2min; then heating power is increased to 400kW, and the heating power is stabilized for 5min; starting an induction coil at the bottom of the crucible, adding heating power to 80kW, and stabilizing for 2min; after the alloy is melted, the power of the main induction coil is reduced to 250kW, and the power of the induction coil at the bottom of the crucible is reduced to 70kW, so that the melt is in a semi-solidification state; the power of the main induction coil is added to 300kW, the power of the induction coil at the bottom of the crucible is added to 90kW, and the heating power of 10kW is added after the temperature of the melt reaches liquidus line; and reducing the power of the main induction coil to the lowest within three seconds, reducing the power of the induction coil at the bottom of the crucible to the lowest within three seconds after the upper part of the melt is solidified, and then turning off the heating power supply. Repeatedly smelting for 4 times to obtain the Ti 24Zr46Nb28Al2 refractory multi-principal element alloy.
The top and the bottom are respectively sampled and then subjected to morphology characterization, the components of the Ti 24Zr46Nb28Al2 refractory multi-principal element alloy are uniform and accurate, the equiaxed structure is taken as the main material, the structure is uniform, the crystal grains are fine, and the mechanical property is excellent. Specifically, the top grain size was 345 μm and the bottom grain size was 295 μm.
Example 2
A method for preparing a Ti 24Zr58Nb18 refractory multi-element alloy with a uniform equiaxed fine grain structure, comprising the steps of:
(1) Raw materials with total mass of (1500+/-0.1) g are weighed according to atomic percent Ti: zr: nb=24:58:18, and clean elemental elements Ti, zr and Nb are uniformly placed in a smelting crucible, wherein low-melting-point elemental metals are placed at the bottom of the crucible, and the elemental metal with the highest melting point is placed in the middle area of the crucible;
(2) Vacuumizing the vacuum suspension cold crucible smelting furnace, and filling high-purity argon as protective gas after the vacuum degree in the furnace body reaches the high vacuum standard. And (3) carrying out alloying smelting by adopting an induction smelting furnace, wherein the protective gas is argon during smelting. The vacuum degree of the smelting chamber is less than or equal to 1 multiplied by 10 -2 Pa.
(3) Starting a main induction coil to perform alloying smelting, gradually increasing power, firstly adding heating power to 100kW, and stabilizing for 3min; secondly, heating power is increased to 180Kw, and the temperature is stabilized for 3min; and finally, heating power is increased to 400kW, and heating power is stabilized for 5min.
(4) Starting an induction coil at the bottom of the crucible, gradually increasing the power, firstly adding the heating power to 20kW, and stabilizing for 3min; then heating power is increased to 40kW, and the heating power is stabilized for 3min; and finally, heating power is increased to 70kW, the temperature is stabilized for 2min, and the alloy melt is completely separated from the crucible wall.
(5) After the alloy is melted, the power of the main induction coil is reduced to 200kW, the power of the induction coil at the bottom of the crucible is reduced to 50kW, the temperature of the melt is reduced to below the liquidus line, the melt is in a semi-solidification state, and the melt is stabilized for 2min.
(6) The power of the main induction coil is added to 250kW, the power of the induction coil at the bottom of the crucible is added to 80kW, the temperature of the melt reaches liquidus, and after the melt is liquefied again, the heating power is increased by 5kW again, and the temperature is stabilized for 2min.
(7) And firstly, reducing the power of the main induction coil to the minimum in three seconds, and after the upper part of the melt is solidified, reducing the power of the induction coil at the bottom of the crucible to the minimum in three seconds, and then, turning off a heating power supply to obtain the alloy ingot cooled to the room temperature.
(8) And (5) heating and smelting the cast ingot again. Firstly, heating power of a main induction coil is added to 100kW, and the main induction coil is stabilized for 2min; then heating power is increased to 300kW, and the heating power is stabilized for 5min; starting an induction coil at the bottom of the crucible, adding heating power to 70kW, and stabilizing for 2min; after the alloy is melted, the power of the main induction coil is reduced to 200kW, and the power of the induction coil at the bottom of the crucible is reduced to 50kW, so that the melt is in a semi-solidification state and is stable for 1min; the power of the main induction coil is added to 250kW, the power of the induction coil at the bottom of the crucible is added to 80kW, and after the temperature of the melt reaches liquidus, the heating power of 5kW is added, and the temperature is stabilized for 1min; and reducing the power of the main induction coil to the lowest within three seconds, reducing the power of the induction coil at the bottom of the crucible to the lowest within three seconds after the upper part of the melt is solidified, and then turning off the heating power supply. Repeatedly smelting for 4 times to obtain the Ti 24Zr58Nb18 refractory multi-principal element alloy.
The top and the bottom are respectively sampled and then subjected to morphology characterization, the components of the Ti 24Zr58Nb18 refractory multi-principal element alloy are uniform and accurate, the equiaxed structure is taken as the main material, the structure is uniform, the crystal grains are fine, and the mechanical property is excellent. Specifically, the top grain size was 334 μm and the bottom grain size was 282 μm.
Example 3
A method for preparing a Ti 24Zr46Nb28O2 refractory multi-element alloy with a uniform equiaxed fine grain structure, comprising the steps of:
(1) Weighing raw materials with total mass of (1500+/-0.1) g according to atomic percent of Ti, zr, nb, O=24, 46, 28 and 2, uniformly placing clean simple substance elements Ti, zr, nb, O into a smelting crucible, wherein low-melting-point simple substance metals are placed at the bottom of the crucible, the simple substance metal with the highest melting point is placed in the middle area of the crucible, and the rest simple substance elements are uniformly placed in the crucible;
(2) Vacuumizing the vacuum suspension cold crucible smelting furnace, and filling high-purity argon as protective gas after the vacuum degree in the furnace body reaches the high vacuum standard. And (3) carrying out alloying smelting by adopting an induction smelting furnace, wherein the protective gas is argon during smelting. The vacuum degree of the smelting chamber is less than or equal to 1 multiplied by 10 -2 Pa.
(3) Starting a main induction coil to perform alloying smelting, gradually increasing power, firstly adding heating power to 120kW, and stabilizing for 2min; secondly, heating power is increased to 200Kw, and the temperature is stabilized for 2min; and finally, heating power is increased to 400kW, and heating power is stabilized for 3min.
(4) Starting an induction coil at the bottom of the crucible, increasing the power step by step, firstly adding heating power to 30kW, and stabilizing for 2min; then heating power is increased to 50kW, and the heating power is stabilized for 2min; and finally, heating power is increased to 80kW, the temperature is stabilized for 1min, and the alloy melt is completely separated from the crucible wall.
(5) After the alloy is melted, the power of the main induction coil is reduced to 250kW, the power of the induction coil at the bottom of the crucible is reduced to 70kW, the temperature of the melt is reduced to below the liquidus line, and the melt is in a semi-solidification state and is maintained for 1min.
(6) The power of the main induction coil is added to 300kW, the power of the induction coil at the bottom of the crucible is added to 100kW, the temperature of the melt reaches liquidus, and after the melt is liquefied again, the heating power is increased by 10kW again and maintained for 1min.
(7) And firstly, reducing the power of the main induction coil to the minimum in three seconds, and after the upper part of the melt is solidified, reducing the power of the induction coil at the bottom of the crucible to the minimum in three seconds, and then, turning off a heating power supply to obtain the alloy ingot cooled to the room temperature.
(8) And (5) heating and smelting the cast ingot again. Firstly, heating power of a main induction coil is added to 120kW, and the main induction coil is stabilized for 1min; then heating power is increased to 400kW, and the heating power is stabilized for 3min; starting an induction coil at the bottom of the crucible, adding heating power to 80kW, and stabilizing for 1min; after the alloy is melted, the power of the main induction coil is reduced to 250kW, the power of the induction coil at the bottom of the crucible is reduced to 70kW, and the melt is in a semi-solidification state and is maintained for 1min; the power of the main induction coil is added to 300kW, the power of the induction coil at the bottom of the crucible is added to 90kW, and the heating power of 10kW is added after the temperature of the melt reaches liquidus line; and reducing the power of the main induction coil to the lowest within three seconds, reducing the power of the induction coil at the bottom of the crucible to the lowest within three seconds after the upper part of the melt is solidified, and then turning off the heating power supply. Repeatedly smelting for 4 times to obtain the Ti 24Zr46Nb28O2 refractory multi-principal element alloy.
The top and the bottom are respectively sampled and then subjected to morphology characterization, the components of the Ti 24Zr46Nb28O2 refractory multi-principal element alloy are uniform and accurate, the equiaxed structure is taken as the main material, the structure is uniform, the crystal grains are fine, and the mechanical property is excellent. Specifically, the top grain size was 352 μm and the bottom grain size was 298 μm. Example 4
A method for preparing a Ti 30Zr55Nb15 refractory multi-element alloy with a uniform equiaxed fine grain structure, comprising the steps of:
(1) Raw materials with total mass of (1500+/-0.1) g are weighed according to atomic percent Ti: zr: nb=30:55:15, clean treated elemental elements Ti, zr, nb, al are uniformly placed in a smelting crucible, wherein low-melting elemental metal is placed at the bottom of the crucible, elemental metal with the highest melting point is placed in the middle area of the crucible, and the rest elemental elements are uniformly placed in the crucible;
(2) Vacuumizing the vacuum suspension cold crucible smelting furnace, and filling high-purity argon as protective gas after the vacuum degree in the furnace body reaches the high vacuum standard. And (3) carrying out alloying smelting by adopting an induction smelting furnace, wherein the protective gas is argon during smelting. The vacuum degree of the smelting chamber is less than or equal to 1 multiplied by 10 -2 Pa.
(3) Starting a main induction coil to perform alloying smelting, gradually increasing power, firstly adding heating power to 100kW, and stabilizing for 2min; secondly, heating power is increased to 180Kw, and the temperature is stabilized for 2min; and finally, heating power is increased to 300kW, and heating power is stabilized for 3min.
(4) Starting an induction coil at the bottom of the crucible, increasing the power step by step, firstly adding the heating power to 20kW, and stabilizing for 2min; then heating power is increased to 40kW, and the heating power is stabilized for 2min; and finally, heating power is increased to 70kW, the temperature is stabilized for 1min, and the alloy melt is completely separated from the crucible wall.
(5) After the alloy is melted, the power of the main induction coil is reduced to 200kW, the power of the induction coil at the bottom of the crucible is reduced to 50kW, the temperature of the melt is reduced to below the liquidus line, the melt is in a semi-solidification state, and the temperature is maintained for 1min.
(6) The main induction coil power is added to 250kW, the crucible bottom induction coil power is added to 80kW, the temperature of the melt reaches liquidus, and after the melt is re-liquefied, the heating power is increased by 5kW again, and the temperature is maintained for 1min.
(7) And firstly, reducing the power of the main induction coil to the minimum in three seconds, and after the upper part of the melt is solidified, reducing the power of the induction coil at the bottom of the crucible to the minimum in three seconds, and then, turning off a heating power supply to obtain the alloy ingot cooled to the room temperature.
(8) And (5) heating and smelting the cast ingot again. Firstly, heating power of a main induction coil is added to 100kW, and the main induction coil is stabilized for 1min; then heating power is increased to 300kW, and the heating power is stabilized for 3min; starting an induction coil at the bottom of the crucible, adding heating power to 70kW, and stabilizing for 1min; after the alloy is melted, the power of the main induction coil is reduced to 200kW, and the power of the induction coil at the bottom of the crucible is reduced to 50kW, so that the melt is in a semi-solidification state; the power of the main induction coil is added to 250kW, the power of the induction coil at the bottom of the crucible is added to 80kW, and the heating power of 5kW is added after the temperature of the melt reaches liquidus line; and reducing the power of the main induction coil to the lowest within three seconds, reducing the power of the induction coil at the bottom of the crucible to the lowest within three seconds after the upper part of the melt is solidified, and then turning off the heating power supply. Repeatedly smelting for 4 times to obtain the Ti 30Zr55Nb15 refractory multi-principal element alloy.
The top and the bottom are respectively sampled and then subjected to morphology characterization, the components of the Ti 30Zr55Nb15 refractory multi-principal element alloy are uniform and accurate, the equiaxed structure is taken as the main material, the structure is uniform, the crystal grains are fine, and the mechanical property is excellent. Specifically, the top grain size was 363 μm and the bottom grain size was 311 μm.
Comparative example 1
Based on the embodiment 1, the process of the last smelting is changed into: firstly, heating power of a main induction coil is added to 120kW, and the main induction coil is stabilized for 2min; then heating power is increased to 400kW, and the heating power is stabilized for 5min; starting an induction coil at the bottom of the crucible, adding heating power to 80kW, and stabilizing for 2min; after the alloy is melted, the power of the main induction coil is reduced to 250kW, and the power of the induction coil at the bottom of the crucible is reduced to 70kW, so that the melt is in a semi-solidification state; the power of the main induction coil is added to 300kW, the power of the induction coil at the bottom of the crucible is added to 90kW, and the heating power of 30kW is increased after the temperature of the melt reaches liquidus line; and reducing the power of the main induction coil to the lowest within three seconds, reducing the power of the induction coil at the bottom of the crucible to the lowest within three seconds after the upper part of the melt is solidified, and then turning off a heating power supply to obtain the multi-principal element alloy cast ingot.
The morphology characterization shows that the alloy has an equiaxed crystal structure and coarse grain size. Specifically, the top grain size was 534 μm and the bottom grain size was 463 μm.
Comparative example 2
Based on the embodiment 1, the process of the last smelting is changed into: firstly, heating power of a main induction coil is added to 120kW, and the main induction coil is stabilized for 2min; then heating power is increased to 400kW, and the heating power is stabilized for 5min; starting an induction coil at the bottom of the crucible, adding heating power to 80kW, and stabilizing for 2min; after the alloy is melted, the power of the main induction coil is reduced to 250kW, and the power of the induction coil at the bottom of the crucible is reduced to 70kW, so that the melt is in a semi-solidification state; the power of the main induction coil is added to 300kW, the power of the induction coil at the bottom of the crucible is added to 90kW, and the heating power is maintained unchanged after the temperature of the melt reaches liquidus line; and reducing the power of the main induction coil to the lowest within three seconds, reducing the power of the induction coil at the bottom of the crucible to the lowest within three seconds after the upper part of the melt is solidified, and then turning off a heating power supply to obtain the multi-principal element alloy cast ingot.
Through morphological characterization, the alloy is in an equiaxed crystal structure, but because the suspension force at the bottom of the crucible is insufficient, the heat of the adhesion of the melt is quickly lost, so that the grain size at the bottom of the ingot is obviously smaller than that at the top of the ingot, and the structure is uneven. Specifically, the top grain size was 437 μm and the bottom grain size was 280 μm.
Comparative example 3
Based on the embodiment 1, the process of the last smelting is changed into: firstly, heating power of a main induction coil is added to 120kW, and the main induction coil is stabilized for 2min; then heating power is increased to 400kW, and the heating power is stabilized for 5min; starting an induction coil at the bottom of the crucible, adding heating power to 80kW, and stabilizing for 2min; after the alloy is melted, reducing the power of the main induction coil to 200-250 kW, and reducing the power of the induction coil at the bottom of the crucible to 70kW, so that the melt is in a semi-solidification state; the power of the main induction coil is added to 300kW, the power of the induction coil at the bottom of the crucible is added to 90kW, and the heating power of 10kW is added after the temperature of the melt reaches liquidus line; and simultaneously reducing the power of the main induction coil and the power of the induction coil at the bottom of the crucible to the lowest within three seconds, and turning off the heating power supply to obtain the multi-principal element alloy cast ingot.
The morphology characterization shows that the alloy is in an equiaxed crystal structure, but the heat loss is faster due to the large adhesion area of the melt at the bottom of the crucible, so that the grain size at the bottom of the ingot is obviously smaller than that at the top of the ingot, and the structure is uneven. Specifically, the top grain size is 496 μm and the bottom grain size is 350 μm.
Comparative example 4
Based on the embodiment 1, the process of the last smelting in the embodiment 1 is changed to: firstly, heating power of a main induction coil is added to 120kW, and the main induction coil is stabilized for 2min; then heating power is increased to 400kW, and the heating power is stabilized for 5min; starting an induction coil at the bottom of the crucible, adding heating power to 80kW, and stabilizing for 2min; after the alloy is melted, the power of the main induction coil is reduced to 250kW, and the power of the induction coil at the bottom of the crucible is reduced to 70kW, so that the melt is in a semi-solidification state; the power of the main induction coil is added to 300kW, the power of the induction coil at the bottom of the crucible is added to 90kW, and the heating power of 10kW is added after the temperature of the melt reaches liquidus line; and reducing the power of the main induction coil to the lowest within fifteen seconds, reducing the power of the induction coil at the bottom of the crucible to the lowest within fifteen seconds after the upper part of the melt is solidified, and then turning off a heating power supply to obtain the multi-principal element alloy cast ingot.
The morphology characterization shows that the alloy has an equiaxed crystal structure, but the overheating degree is slowly reduced during solidification, and the crystal grains are rapidly grown, so that the crystal grains of the obtained alloy are coarse in size. Specifically, the top grain size is 510 μm and the bottom grain size is 498 μm.
Therefore, the method ensures that the melt at the bottom of the crucible obtains enough heat and levitation force through the power matching of the main induction coil and the induction coil at the bottom of the crucible, avoids the excessive heat loss caused by the contact of the melt and the crucible wall, reduces the integral temperature gradient of the melt, improves the uniformity of temperature distribution in the melt, and ensures the uniformity of tissues at different positions of the cast ingot.
In view of the foregoing, it will be appreciated that the invention includes but is not limited to the foregoing embodiments, any equivalent or partial modification made within the spirit and principles of the invention.
Claims (9)
1. A preparation method of a TiZrNb-series refractory multi-principal element alloy with uniform equiaxed fine grain structure is characterized by comprising the following steps: the method comprises the following steps:
(1) Placing a TiZrNb series refractory multi-element alloy raw material into a water-cooled copper crucible of a vacuum suspension smelting furnace; vacuumizing the vacuum suspension smelting furnace and filling protective gas;
(2) Firstly starting a main induction coil to gradually increase and maintain the power, and then starting an induction coil at the bottom of a crucible to gradually increase and maintain the power for alloying smelting;
(3) After the alloy is melted, reducing the power of the main induction coil and the induction coil at the bottom of the crucible, so that the temperature of the melt is reduced to be between a liquidus line and a solidus line, the melt is in a semi-solidification state, and the melt is stabilized for 1-2 min;
(4) The power of the main induction coil and the power of the induction coil at the bottom of the crucible are increased, so that the temperature of the alloy melt reaches liquidus, after the melt is liquefied again, the power of the main induction coil and the power of the induction coil at the bottom of the crucible are respectively increased by 5-10 kW, and the temperature is stabilized for 1-2 min;
(5) Closing the power of the main induction coil within 5 seconds, maintaining the power of the induction coil at the bottom of the crucible, closing the power of the induction coil at the bottom of the crucible within 5 seconds after the upper part of the melt is solidified, and cooling;
(6) Repeating the steps (2) to (5), and repeatedly smelting for more than three times to obtain a TiZrNb refractory multi-principal-element alloy cast ingot after smelting is finished;
Wherein the chemical formula of the TiZrNb refractory multi-element alloy is Ti aZrbNbcMxNy, M is more than one of Al, cr, mn, fe, cu, ni, mo, W, N is more than one of B, C, N, O, si, a is more than or equal to 10 and less than or equal to 60,5 and less than or equal to b and less than or equal to 60, c is more than or equal to 15 and less than or equal to 75,0 and less than or equal to x and less than or equal to 10, y is more than or equal to 0 and less than or equal to 5, and a+b+c+x+y=100.
2. A method of producing a TiZrNb-based refractory multi-principal component alloy having a uniform equiaxed fine grain structure according to claim 1, wherein: a is more than or equal to 15 and less than or equal to 30, b is more than or equal to 5 and less than or equal to 60, c is more than or equal to 15 and less than or equal to 75,0 and less than or equal to x is more than or equal to 10, y is more than or equal to 0 and less than or equal to 5, and a+b+c+x+y=100.
3. A method of producing a TiZrNb-based refractory multi-master alloy having a uniform equiaxed fine grain structure according to claim 1 or 2, wherein: in the step (1), the shielding gas is an inert gas.
4. A method of producing a TiZrNb-based refractory multi-master alloy having a uniform equiaxed fine grain structure according to claim 1 or 2, wherein: in the step (2), the power of the main induction coil is started to be 100-120 kW, the power is stabilized for 2-3 min, the power is increased to be 180-200 kW, the power is stabilized for 2-3 min, the power is increased to be 300-400 kW, and the heating power is stabilized for 3-5 min; starting an induction coil at the bottom of the crucible to 20-30 kW, stabilizing for 2-3 min, improving to 40-50 kW, stabilizing for 2-3 min, improving to 70-80 kW, and stabilizing for 1-2 min.
5. A method of producing a TiZrNb-based refractory multi-master alloy having a uniform equiaxed fine grain structure according to claim 1 or 2, wherein: in the step (3), the power of the main induction coil is reduced to 200-250 kW, and the power of the induction coil at the bottom of the crucible is reduced to 50-60 kW.
6. A method of producing a TiZrNb-based refractory multi-master alloy having a uniform equiaxed fine grain structure according to claim 1 or 2, wherein: in the step (4), the power of the main induction coil is increased to 250-300 kW, and the power of the induction coil at the bottom of the crucible is increased to 80-100 kW.
7. A method of producing a TiZrNb-based refractory multi-master alloy having a uniform equiaxed fine grain structure according to claim 1 or 2, wherein: in the step (6), when the steps (2) to (5) are repeated, starting the power of the main induction coil to 100-120 kW, and stabilizing for 1-2 min; raising the temperature to 300-400 kW, and stabilizing for 3-5 min; starting the power of an induction coil at the bottom of the crucible to 70-80 kW, and stabilizing for 1-2 min; after the alloy is melted, reducing the power of the main induction coil to 200-250 kW, reducing the power of the induction coil at the bottom of the crucible to 50-60 kW, and stabilizing the melt in a semi-solidification state for 1-2 min; the power of the main induction coil is increased to 250-300 kW, the power of the induction coil at the bottom of the crucible is increased to 80-90 kW, after melt is liquefied again, the power of the main induction coil and the power of the induction coil at the bottom of the crucible are respectively increased by 5-10 kW, and the stability is kept for 1-2 min; and closing the power of the main induction coil within 5 seconds, maintaining the power of the induction coil at the bottom of the crucible, closing the power of the induction coil at the bottom of the crucible within 5 seconds after the upper part of the melt is solidified, and cooling.
8. A method of producing a TiZrNb-based refractory multi-principal component alloy having a uniform equiaxed fine grain structure according to claim 7, wherein: in the step (6), the smelting is repeated three to four times.
9. A TiZrNb-based refractory multi-principal element alloy having a uniform equiaxed fine grain structure, characterized by: the method according to any one of claims 1 to 8.
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