CN116358962A - Preparation method of CoFeNi medium-entropy alloy tensile sample under deep supercooling condition - Google Patents
Preparation method of CoFeNi medium-entropy alloy tensile sample under deep supercooling condition Download PDFInfo
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- G01N1/00—Sampling; Preparing specimens for investigation
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Abstract
The invention provides a preparation method of a CoFeNi medium entropy alloy tensile sample under a deep supercooling condition, wherein the alloy deep supercooling process of the preparation method is carried out by a high-frequency induction heating device and a mode of combining a melt dipping method and a circulating overheat method, the smelting process firstly sequentially places single substances of all alloy raw materials into a quartz crucible from bottom to top according to a sequence from high melting point to low melting point, and adds glass purifying agents into the lowest layer and the uppermost layer of the alloy raw materials, and during smelting, the glass purifying agents are sequentially melted and coated on the alloy surface, the melting of Ni metal raw materials and the melting of other metal raw materials by controlling the vertical movement of the quartz crucible in the central axis direction of a high-frequency induction coil and the heating temperature of the high-frequency induction coil, the alloy liquid is sufficiently mixed, cooled and solidified, and repeatedly heated, cooled and solidified until 205K supercooling degree is obtained, so that a CoFeNi medium entropy alloy ingot meeting the tensile test size is prepared. The invention has the advantages of easy control of the solidification process, mature process and small component loss.
Description
Technical Field
The application belongs to the technical field of alloy preparation, and particularly relates to a preparation method of a CoFeNi medium entropy alloy tensile sample under a deep supercooling condition.
Background
The medium entropy alloy is an alloy composed of three elements in equimolar or nearly equimolar ratio, and the composition characteristics of the medium entropy alloy lead the medium entropy alloy to have high strength, high hardness, good wear resistance, high resistivity, excellent corrosion resistance, excellent magnetic property, good hydrogen storage property and the like, so that the medium entropy alloy has great interest in the alloy systems.
Of these, coFeNi is a single-phase disordered solid solution alloy with FCC crystal structure, exhibiting lower yield strength. At present, most of researches adopt an arc melting device to prepare CoFeNi alloy ingots, coarse grains are easy to form, the mechanical properties of the alloy and the like are adversely affected, and the application of the alloy as a structural material is limited. Compared with the equilibrium solidification process such as arc melting, the rapid solidification process can obviously reduce the generation of structural defects and refine grains. The dendrite growth and solidification mechanism of alloys under deep supercooling conditions has been receiving extensive attention from researchers for many years, and the thermodynamic and kinetic theory of metal melts under deep supercooling rapid solidification conditions has been matured. The Chinese patent office publication number CN 103643063A, patent name: the patent adopts a method of combining molten glass purification, temperature control and glass purifying agent cleaning and purifying to realize deep supercooling solidification of the multi-element alloy, and a button alloy ingot with the mass of 30/120g is obtained, and the size still cannot meet the tensile mechanical test size. Chinese patent office publication number CN1552544a, patent name: the patent proposes a method for preparing directional alloy materials by combining molten glass purification and cyclic overheating, wherein the preparation process requires that a first quartz tube is leaked into a second quartz tube after reaching a softening point, and the method has a certain rejection rate.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and provides a preparation method of an entropy alloy tensile sample in CoFeNi under a deep supercooling condition, so that the difficult problem of insufficient height of the tensile sample is solved.
The invention is realized by the method, the alloy deep supercooling process of the preparation method is carried out by a high-frequency induction heating device and adopting a mode of combining a melt dipping and floating method and a circulating overheat method, the smelting process firstly sequentially puts the elementary substances of all alloy raw materials into a quartz crucible from bottom to top according to the sequence of melting points, and adds glass purifying agents into the lowest layer and the uppermost layer of the alloy raw materials, and the glass purifying agents are sequentially melted and coated on the alloy surface, the melting of Ni metal raw materials and the melting of other metal raw materials by controlling the vertical movement of the quartz crucible in the central axis direction of a high-frequency induction coil and the heating temperature of the high-frequency induction coil during smelting, the alloy liquid is cooled and solidified after being fully mixed, and the heating and the cooling solidification are repeated until 205K supercooling degree is obtained, so that the alloy ingot in CoFeNi meeting the stretching test size is prepared.
The invention is also characterized in that the preparation method comprises the following steps:
step 1, batching: taking elementary substances of each element as raw materials, and according to the mole percentage Co of each element of the entropy alloy in CoFeNi: fe: ni=1: 1:1, weighing each metal simple substance, and configuring raw materials;
step 2, discharging: selecting a quartz crucible with a cylindrical upper end opening, sequentially placing the prepared raw materials into the quartz crucible, and laying the raw materials into the quartz crucible from bottom to top according to the order of glass purifying agents, fe, co, ni and glass purifying agents when the raw materials are placed;
step 3, crucible position adjustment: an electric push rod device is adopted to control the quartz crucible to vertically move up and down along the central axis direction of the high-frequency induction coil, so that the contact surface of the glass purifying agent at the upper part of the quartz crucible and the Ni simple substance is positioned at an effective heating position in the vertical direction of the high-frequency induction coil;
step 4, vacuumizing: after closing the vacuum cavity door, starting the cold water machine, and pumping the vacuum degree in the vacuum arc cavity to 10 -3 After Pa and above, closing the air extraction valve, opening the air inlet valve, reversely filling high-purity argon into the cavity to 0.5 standard atmospheric pressure, and closing the air inlet valve;
step 5: heating the alloy to 1073-1173 ℃ by a high-frequency induction coil, observing the softening condition of the glass purifying agent by a high-speed CCD, and preserving the heat for 1min to enable the glass purifying agent to be fused and coated on the surface of the alloy;
step 6: heating to 1400-1500 ℃, then preserving heat for 1min to ensure that the Ni metal simple substance is completely melted;
step 7: heating to 1650-1850 ℃, controlling an electric push rod device to enable the quartz crucible to move upwards, melting Co and Fe metal simple substances through high-frequency induction heating and heat conduction between metals, stopping moving the quartz crucible after complete melting, preserving heat for 2min, fully mixing alloy liquid by virtue of electromagnetic stirring, and closing high frequency for cooling solidification;
step 8: observing a temperature curve acquired by an infrared probe, and opening high frequency to continue heating when the temperature is reduced to 850-900 ℃;
step 9: rapidly heating to 1650-1850 ℃, preserving heat for 1min, and closing high frequency to cool and solidify;
step 10: and (3) repeating the steps 8 and 9 until the supercooling degree of 205K is obtained, cooling for 3 hours, and taking out a cylindrical CoFeNi alloy sample with uniform components.
The invention is also characterized in that the quartz crucible used has the specification of inner diameter: 16mm, outer diameter: 20mm, height: 100mm, the addition height of the alloy raw material is 4/5 of the height of the quartz crucible.
The invention is also characterized in that the total amount of the alloy raw materials is 60g, and the total amount of the glass purifying agent is 9-10g.
The invention is also characterized in that one end of an electric push rod of the electric push rod device is connected with a crucible base made of boron nitride, a quartz crucible is placed on the crucible base, and the electric push rod device is electrically connected with an external control switch for controlling the quartz crucible to move up and down along the central axis direction of the high-frequency induction coil.
The invention is also characterized in that the length of the obtained cylindrical CoFeNi alloy sample reaches more than 30 mm.
The invention is also characterized in that the glass purifying agent is used as the main component Na 2 O·CaO·6SiO 2 Is a glass of (a).
The invention adopts the melt dipping and floating technology as a deep supercooling preparation means, and utilizes the mode of immersing alloy melt into purifying agent to solidify so as to realize the deep supercooling rapid solidification of the liquid alloy, the solidification process is easy to control, the process is mature, and the component loss is small. A cylindrical quartz crucible is used in the sample preparation process, the quartz crucible filled with raw materials is controlled to move up and down through a point push rod device, so that the melting, purification and large supercooling degree of the metal raw materials are ensured, and a large-size CoFeNi alloy sample meeting the in-situ tensile test size requirement can be obtained.
The present invention will be described in further detail with reference to the accompanying drawings.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, a brief description will be given below of the drawings that are needed in the embodiments or the prior art descriptions, and it is obvious that the drawings in the following description are some embodiments of the present application, and that other drawings can be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram of a quartz crucible and sample loading for use in a deep supercooling test.
FIG. 2 is a drawing showing the cut size of a tensile sample of CoFeNi alloy of 205K supercooling degree prepared in example 1.
FIG. 3 is a graph showing stress strain at room temperature for a 205K supercooled CoFeNi alloy prepared in example 1.
Detailed Description
For the purposes of making the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions in the embodiments of the present application are clearly and completely described below, and it is obvious that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by one of ordinary skill in the art without inventive effort, are also within the scope of the present application based on the embodiments herein.
The following detailed description, structural features and functions of the present invention are provided with reference to the accompanying drawings and examples in order to further illustrate the technical means and effects of the present invention to achieve the predetermined objects.
The embodiment of the invention provides a preparation method of an entropy alloy tensile sample in CoFeNi under a deep supercooling condition, the alloy deep supercooling process of the preparation method is carried out by a high-frequency induction heating device and adopting a mode of combining a melt dipping and floating method and a circulating overheat method, the smelting process firstly sequentially places single substances of all alloy raw materials into a quartz crucible from bottom to top according to the sequence of melting points from top to bottom, and adds a glass purifying agent into the lowest layer and the uppermost layer of the alloy raw materials, and during smelting, the glass purifying agent is sequentially melted and coated on the alloy surface, the melting of Ni metal raw materials and the melting of other metal raw materials by controlling the vertical movement of the quartz crucible in the central axis direction of a high-frequency induction coil and the heating temperature of the high-frequency induction coil, the alloy liquid is sufficiently mixed, cooled and solidified, and repeatedly heated, cooled and solidified until 205K supercooling degree is obtained, so that an entropy alloy ingot in CoFeNi meeting the tensile test size is prepared.
Example 1: preparation of CoFeNi medium entropy alloy tensile sample under deep supercooling condition
The method comprises the following specific steps:
step 1, batching: taking elementary substances of each element as raw materials, and according to the mole percentage Co of each element of the entropy alloy in CoFeNi: fe: ni=1: 1:1, weighing each metal simple substance, and configuring 60g of raw materials; the metal simple substance is metal particles respectively corresponding to Co, fe and Ni elements;
step 2, discharging: a quartz crucible with a cylindrical upper end opening is selected, and the specification of the quartz crucible is as follows: 16mm, outer diameter: 20mm, height: 100mm, and sequentially placing the prepared raw materials into a quartz crucible; when the raw materials are placed, the raw materials are laid into a quartz crucible from bottom to top according to the sequence of the glass purifying agent, fe, co, ni and the glass purifying agent; wherein, the lowest layer in the quartz crucible is paved with glass purifying agent with the thickness of 5mm, the total amount of the glass purifying agent is 9-10g, the adding height of the alloy raw material is 4/5 of the height of the quartz crucible, optionally, the glass purifying agent is glass with the main component of Na2O.CaO.6SiO2, and the glass purifying agent can completely cover the metal raw material after being completely melted;
step 3, crucible position adjustment: an electric push rod device is adopted to control the quartz crucible to vertically move up and down along the central axis direction of the high-frequency induction coil, in order to ensure that the raw materials are completely melted and obtain a large supercooling degree, the contact surface of the upper purifying agent and the Ni simple substance in the quartz crucible is placed at the central position in the vertical direction of the high-frequency coil, so that the contact surface of the glass purifying agent and the Ni simple substance in the upper part of the quartz crucible is positioned at an effective heating position in the vertical direction of the high-frequency induction coil, and in FIG. 1, a schematic diagram of the quartz crucible and a sample loading diagram is adopted, so that effective heating can be ensured; one end of an electric push rod of the electric push rod device is connected with a crucible base made of boron nitride, a quartz crucible is placed on the crucible base, and the electric push rod device is electrically connected with an external control switch for regulating and controlling the quartz crucible to move up and down along the central shaft direction of the high-frequency induction coil;
step 4, vacuumizing: after closing the vacuum cavity door, starting the cold water machine, and pumping the vacuum degree in the vacuum arc cavity to 10 -3 After Pa and above, closing the air extraction valve, opening the air inlet valve, reversely filling high-purity argon into the cavity to 0.5 standard atmospheric pressure, and closing the air inlet valve;
step 5: heating the alloy to 1073-1173 ℃ by a high-frequency induction coil, observing the softening condition of the glass purifying agent by a high-speed CCD, and preserving the heat for 1min to enable the glass purifying agent to be fused and coated on the surface of the alloy; the heating process in the stage can ensure that the purifying agent is melted and wraps the uppermost Ni metal raw material, so that the purifying agent is prevented from being oxidized when in contact with air;
step 6: heating to 1400-1500 ℃, melting and flowing down part of Ni metal particles, and then preserving heat for 1min to ensure that the Ni metal simple substance is completely melted;
step 7: heating to 1650-1850 ℃, and enabling the liquid melt Ni to start flowing downwards under the action of gravity and cover the Co metal raw material, so that the temperature around the Co metal is increased by means of heat radiation and heat conduction, and the melting of the Co metal raw material is accelerated; controlling an electric push rod device to enable the quartz crucible to move upwards, melting Co and Fe metal simple substances through high-frequency induction heating and heat conduction between metals, stopping moving the quartz crucible until complete melting, preserving heat for 2min, fully mixing alloy liquid by means of electromagnetic stirring, and closing high frequency for cooling and solidification;
step 8: observing a temperature curve acquired by an infrared probe, and opening high frequency to continue heating when the temperature is reduced to 850-900 ℃;
step 9: rapidly heating to 1650-1850 ℃, preserving heat for 1min, and closing high frequency to cool and solidify;
step 10: and (3) repeating the steps 8 and 9 until the supercooling degree of 205K is obtained, cooling for 3 hours, taking out a cylindrical CoFeNi alloy sample with uniform components, finally obtaining a cylindrical CoFeNi medium entropy alloy ingot with the diameter of 15.5mm and the height of 37mm, meeting the requirement of the size of a tensile sample, and processing the ingot according to the cutting size schematic diagram of the tensile sample of the CoFeNi alloy with the supercooling degree of 205K, which is prepared in the embodiment, shown in the figure 2. FIG. 3 is a graph showing stress strain at room temperature for the prepared 205K supercooling degree CoFeNi alloy, having a yield strength of 129MPa and a breaking elongation of 40.6%.
The invention adopts the melt dipping and floating technology as a deep supercooling preparation means, and utilizes the mode of immersing alloy melt into purifying agent to solidify so as to realize the deep supercooling rapid solidification of the liquid alloy, the solidification process is easy to control, the process is mature, and the component loss is small. The purification agent in the molten state can remove impurities through the physical action of an interface between the purification agent and the liquid alloy, and meanwhile, the heterogeneous nucleation is passivated by utilizing the chemical reaction of the interface, so that the sample and the container wall are isolated, and the effect of eliminating nucleation catalysis is achieved. A cylindrical quartz crucible is used in the sample preparation process, the quartz crucible filled with raw materials is controlled to move up and down through a point push rod device, so that the melting, purification and large supercooling degree of the metal raw materials are ensured, and a large-size CoFeNi alloy sample meeting the in-situ tensile test size requirement can be obtained. The obtained CoFeNi alloy sample has the size meeting the tensile test requirement, so that the intrinsic mechanism between the mechanical property and the supercooling degree is conveniently researched, and meanwhile, the method can well solve the height problem of the alloy sample and has extremely low rejection rate.
In the embodiment of the invention, the cylindrical specification is selected as the inner diameter: 16mm, outer diameter: 20mm, height: the quartz crucible with the height of 100mm is used for placing metal raw materials, the height of the metal raw materials reaches 4/5 of the height of the quartz crucible, and the high-frequency induction coil cannot fully cover the raw materials to be heated. In order to ensure that the raw materials are completely melted and obtain large supercooling degree, an electric push rod device is adopted to place the uppermost metal raw material in the quartz crucible at the center of a high-frequency induction coil, and cylindrical cast ingots are obtained through smelting. By adopting the quartz crucible with the size, on one hand, the height of the quartz crucible must reach more than 30mm in consideration of the size required by a stretched sample; on the other hand, the difficulty of obtaining large supercooling of the alloy under large volume is increased; therefore, the size of the quartz crucible must be such that a large degree of supercooling is obtained while an ingot of a proper height is melted. In addition, the quartz crucible has good transparency and light transmittance, and has great real-time performance and accuracy for monitoring the high-speed CCD and measuring the temperature of the melt by the infrared thermometer.
The reason why the glass with the main component of Na2O, caO, 6SiO2 is adopted as the purifying agent in the invention is that: the softening point of the glass purifying agent is near 1100K, which is lower than the melting point of each element of the alloy, so that the purifying agent is convenient to coat the alloy surface, and meanwhile, the purifying agent does not react with each element of the alloy, but has good adsorption capacity, can react with oxides or hydroxides of each element, plays a good purifying role, and has good light transmittance, thereby facilitating the temperature acquisition.
Finally, it should be noted that the above embodiments are merely for illustrating the technical solution of the present application, and are not limiting; although the present application has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art will understand; the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the corresponding technical solutions from the scope of the technical solutions of the embodiments of the present application.
Claims (7)
1. The preparation method of the entropy alloy tensile sample in CoFeNi under the deep supercooling condition is characterized in that the alloy deep supercooling process of the preparation method is carried out by a high-frequency induction heating device and adopting a mode of combining a melt dipping method and a circulating overheat method, the smelting process firstly sequentially puts single substances of all alloy raw materials into a quartz crucible from bottom to top according to the sequence of melting point from top to bottom, and adds glass purifying agents into the lowest layer and the uppermost layer of the alloy raw materials, and during smelting, the glass purifying agents are sequentially melted and coated on the alloy surface, the melting of Ni metal raw materials and the melting of other metal raw materials through controlling the vertical movement of the quartz crucible in the central axis direction of a high-frequency induction coil and the heating temperature of the high-frequency induction coil, the alloy liquid is sufficiently mixed, cooled and solidified, and repeatedly heated, cooled and solidified until 205K supercooling degree is obtained, so that the entropy alloy ingot in CoFeNi meeting the tensile test size is prepared.
2. The method for preparing the tensile sample of the entropy alloy in CoFeNi under the deep supercooling condition according to claim 1, which comprises the following steps:
step 1, batching: taking elementary substances of each element as raw materials, and according to the mole percentage Co of each element of the entropy alloy in CoFeNi: fe: ni=1: 1:1, weighing each metal simple substance, and configuring raw materials;
step 2, discharging: selecting a quartz crucible with a cylindrical upper end opening, and sequentially placing the prepared raw materials into the quartz crucible; when the raw materials are placed, the raw materials are laid into a quartz crucible from bottom to top according to the sequence of the glass purifying agent, fe, co, ni and the glass purifying agent;
step 3, crucible position adjustment: an electric push rod device is adopted to control the quartz crucible to vertically move up and down along the central axis direction of the high-frequency induction coil, so that the contact surface of the glass purifying agent at the upper part of the quartz crucible and the Ni simple substance is positioned at an effective heating position in the vertical direction of the high-frequency induction coil;
step 4, vacuumizing: after closing the vacuum cavity door, starting the cold water machine, and pumping the vacuum degree in the vacuum arc cavity to 10 -3 After Pa and above, closing the air extraction valve, opening the air inlet valve, reversely filling high-purity argon into the cavity to 0.5 standard atmospheric pressure, and closing the air inlet valve;
step 5: heating the alloy to 1073-1173 ℃ by a high-frequency induction coil, observing the softening condition of the glass purifying agent by a high-speed CCD, and preserving the heat for 1min to enable the glass purifying agent to be fused and coated on the surface of the alloy;
step 6: heating to 1400-1500 ℃, then preserving heat for 1min to ensure that the Ni metal simple substance is completely melted;
step 7: heating to 1650-1850 ℃, controlling an electric push rod device to enable the quartz crucible to move upwards, melting Co and Fe metal simple substances through high-frequency induction heating and heat conduction between metals, stopping moving the quartz crucible after complete melting, preserving heat for 2min, fully mixing alloy liquid by virtue of electromagnetic stirring, and closing high frequency for cooling solidification;
step 8: observing a temperature curve acquired by an infrared probe, and opening high frequency to continue heating when the temperature is reduced to 850-900 ℃;
step 9: rapidly heating to 1650-1850 ℃, preserving heat for 1min, and closing high frequency to cool and solidify;
step 10: and (3) repeating the steps 8 and 9 until the supercooling degree of 205K is obtained, cooling for 3 hours, and taking out a cylindrical CoFeNi alloy sample with uniform components.
3. The method for preparing a tensile sample of an entropy alloy in CoFeNi under the condition of deep supercooling as claimed in claim 2, wherein the quartz crucible used has an inner diameter of: 16mm, outer diameter: 20mm, height: 100mm, the addition height of the alloy raw material is 4/5 of the height of the quartz crucible.
4. The method for preparing a tensile sample of an entropy alloy in CoFeNi under the condition of deep supercooling as claimed in claim 2, wherein the total amount of the alloy raw material is 60g, and the total amount of the glass purifying agent is 9-10g.
5. The method for preparing the tensile sample of the entropy alloy in CoFeNi under the condition of deep supercooling as claimed in claim 2, wherein one end of an electric push rod of the electric push rod device is connected with a crucible base made of boron nitride, a quartz crucible is placed on the crucible base, and the electric push rod device is electrically connected with an external control switch for controlling the quartz crucible to move up and down along the central axis direction of the high-frequency induction coil.
6. The method for preparing a tensile sample of an entropy alloy in CoFeNi under the condition of deep supercooling as claimed in claim 2, wherein the length of the obtained cylindrical CoFeNi alloy sample is up to 30mm or more.
7. The method for preparing a tensile sample of an entropy alloy in CoFeNi under deep supercooling conditions as claimed in any one of claims 1 to 6, characterized in that a glass scavenger is used as a main component Na 2 O·CaO·6SiO 2 Is a glass of (a).
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