CN110592416A - Plasma-assisted gas alloying method - Google Patents
Plasma-assisted gas alloying method Download PDFInfo
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Abstract
The invention relates to the technical field of metal alloying treatment, in particular to a plasma-assisted gas alloying method, which comprises the steps of putting a metal raw material to be alloyed into a water-cooled crucible of a vacuum arc melting furnace, vacuumizing the vacuum arc melting furnace, introducing mixed gas into the vacuum arc melting furnace to reach a melting pressure value, starting melting, continuing for 2-5 min for one time, cooling for 3min, turning an ingot obtained by melting up and down by 180 degrees to obtain a melting period, repeating for 3-5 melting periods, and obtaining alloying metal containing gas elements after the alloy is fully cooled. According to the invention, gas atoms are diffused into metal by plasma ionization of gas in the metal smelting process, so that the overall service performance or the processing performance of the alloy is improved, and the performance requirements of the material in different service environments and processing processes are met.
Description
Technical Field
The invention relates to the technical field of metal alloying treatment, in particular to a plasma-assisted gas alloying method.
Background
With the rapid development of science and technology, the performance requirements for materials are gradually increased, the traditional alloy is difficult to meet the performance requirements of special conditions, and then an alloying concept is proposed. Alloying refers to the step of alloying a metal into an alloy with desired properties under certain process conditions by adding elements. In order to make the material meet special performance requirements, hydrogen, nitrogen, oxygen, etc. are commonly used alloying gases. For example: hydrogen may improve the hot workability of titanium alloys and titanium aluminum alloys, nitrogen or oxygen may increase the strength of most alloys, and so on.
In the prior art, gas alloying metals are almost all performed in a vacuum furnace under the conditions of high temperature and high pressure by solid metals, the method has higher requirement on equipment, needs special equipment, has slow speed and low energy consumption and efficiency, and has long period for obtaining the gas alloying alloys. Because the gas is diffused in the solid, the alloying uniformity degree is lower, the production cost is increased, and the product percent of pass is not high.
Disclosure of Invention
In order to overcome the technical problems, the invention provides a plasma-assisted gas alloying method, which can form a gas alloying alloy with uniformly distributed alloy elements in the whole alloy ingot in the metal smelting process without designing special alloying equipment, thereby reducing the production cost and shortening the period of alloying metals.
The technical scheme for solving the technical problems is as follows:
a method of plasma assisted gas alloying comprising the steps of:
putting a metal raw material to be alloyed into a water-cooled crucible of a vacuum arc melting furnace, vacuumizing the vacuum arc melting furnace, washing the vacuum arc melting furnace with mixed gas, repeating the gas washing step for 2-3 times, vacuumizing the vacuum arc melting furnace, introducing the mixed gas into the vacuum arc melting furnace to reach a melting pressure value, starting melting, continuing the melting for 2-5 min for one time, continuously introducing the mixed gas during the melting process, cooling for 3min, turning the ingot obtained by melting for 180 degrees up and down to obtain a melting period, repeating the melting period for 3-5 times, and fully cooling the alloy to obtain the alloyed metal containing gas elements.
The vacuum state can avoid impurity atoms in the air to react with metal raw materials and gas alloying elements at a high temperature state, so that the uneven distribution of the alloying elements is avoided, and the metal piece is heated uniformly in the vacuum state, so that the uniform and stable distribution of the gas in the alloy piece is ensured. The purity of the mixed gas in the smelting process can be improved by washing the gas for 2-3 times, and the plasma-assisted gas alloying treatment is facilitated.
The smelting for 2-5 min each time is to ensure that the alloy raw material is fully melted, and the gas has sufficient time to be ionized into (H, O, N) atoms to be diffused into the alloy under the action of plasma. The up-and-down turning can ensure that the alloy components and (H, O, N) atoms are uniformly distributed in the alloy to a certain extent. Smelting for 3-5 times can ensure that (H, O, N) atoms absorbed by the alloy can reach a saturated state.
Further, the metal raw material to be alloyed comprises any one of a titanium alloy, a zirconium alloy, a titanium-aluminum alloy, an iron-based alloy or a high-entropy alloy.
Furthermore, the vacuum degree of the vacuum pumping of the vacuum arc melting furnace is 5 multiplied by 10-3Pa～2Pa。
Further, the mixed gas is X2/Ar2Wherein X is H, O, N.
Furthermore, the mode of introducing the mixed gas into the vacuum arc melting furnace is to adopt high-purity gas (H)2、O2、N2Ar) respectively adjusting the flow rates of different gas storage steel cylinders, introducing the different gas storage steel cylinders into a gas mixing tank, and uniformly mixing the different gas storage steel cylinders, wherein the specific method comprises the following steps:
the plasma-assisted alloying device comprises a gas mixing system, a smelting system and an exhaust system which are sequentially connected, wherein the gas mixing system comprises a gas mixing tank and an H gas mixing tank2、O2、N2The steel bottle is stored to four kinds of gases of Ar, and the exit of every gas storage steel bottle is installed the relief pressure valve, relief pressure valve and gas mixing tank pass through the tetrafluoro pipe connection, all have concatenated high-pressure stop valve and float flowmeter in proper order on every pipeline, through float flowmeter, high-pressure stop valve and the four kinds of gaseous flow that get into the gas mixing tank of relief pressure valve cooperation control, the mist gets into the system of smelting again after mixing the gas tank internal misce bene, after smelting, gets into exhaust system by the outlet duct, exhaust system include exhaust duct, exhaust duct on install a three way valve, three way valve one end connect the vacuum pump, the gas outlet is connected to one end.
Further, the gas mixing tank is provided with a pressure gauge for measuring the gas pressure in the gas mixing tank.
The special ventilation mode has the advantages that the gas in the product is uniformly distributed, the utilization rate of the introduced gas is high, and the gas can be introduced as much as possible, so that the comprehensive performance of final product alloying is improved.
Further, the smelting pressure value is 0.05 MPa.
More specifically, the current in the smelting process is 150-400A.
The invention has the beneficial effects that:
the invention provides a plasma-assisted gas alloying method, which can form gas alloying alloy with uniformly distributed alloy elements in the whole alloy ingot in the metal smelting process without designing special alloying equipment, thereby reducing the production cost and shortening the period of alloying metal.
According to the invention, gas atoms are diffused into metal by plasma ionization of gas in the metal smelting process, so that the overall performance of the alloy is improved, and the performance requirements of the material in different use environments and processing processes are met.
The special ventilation mode is adopted, so that the alloying elements of the product are uniformly distributed. The invention has simple process operation, low equipment requirement and convenient popularization and use.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
FIG. 1 is a schematic view of a gas alloying process in example 1 of the present invention;
FIG. 2 shows TiAl alloys before and after gas alloying treatment in example 1 of the present invention at 1100 ℃ for 0.01s-1Stress strain curve under conditions;
FIG. 3 is a schematic view of a gas alloying process in example 2 of the present invention;
FIG. 4 is a schematic view of a gas alloying process in example 3 of the present invention;
FIG. 5 is a schematic structural view of a plasma-assisted gas alloying apparatus of the present invention;
FIG. 6 shows TiZrHfNbMo alloy before and after gas alloying treatment in example 3 of the present invention at room temperature for 0.01s-1Stress strain curve under conditions;
FIG. 7 is a schematic view of a gas alloying process in example 4 of the present invention;
FIG. 8 is a schematic view of a gas alloying flow in example 5 of the present invention;
fig. 9 shows the titanium alloy before and after the gas alloying treatment of example 5 of the present invention at 850 c,0.01s-1stress strain curve under conditions;
FIG. 10 is a schematic view of a gas alloying flow in example 6 of the present invention;
FIG. 11 shows Zr alloy before and after the gas alloying treatment in example 6 of the present invention at 700 ℃ for 0.01s-1Stress strain curve under conditions.
Detailed Description
Example 1:
the conventional hydrogenation treatment comprises the steps of placing an alloy mother ingot to be treated in a vacuum furnace, firstly carrying out vacuum-pumping treatment to ensure that the interior of the furnace body is in a vacuum state, then heating to a preset heat preservation temperature, adding hydrogen-argon mixed gas into the furnace, and controlling the pressure, the temperature and the flow rate of the mixed gas to achieve the hydrogenation treatment of the alloy. However, the prior hydrogenation treatment process needs matched equipment, so that the production cost is greatly increased, and meanwhile, the manufacturing process of the mother ingot and the hydrogenation treatment are two parts, so that the hydrogenation treatment period is greatly increased.
Based on the above disadvantages, the present embodiment adopts the following method, referring to fig. 1:
the method for alloying TiAl alloy by hydrogen comprises the following specific steps:
placing TiAl alloy raw materials to be alloyed into a water-cooled crucible of a vacuum arc melting furnace, and vacuumizing the vacuum arc melting furnace to the vacuum degree of 5 multiplied by 10-3And Pa, washing the vacuum arc melting furnace with a small amount of hydrogen-argon mixed gas, repeating the gas washing step for 2-3 times, vacuumizing the vacuum arc melting furnace until the vacuum degree is 0.5Pa, introducing the hydrogen-argon mixed gas into the vacuum arc melting furnace until the melting pressure value is 0.05Mpa and the current is 400A, starting melting, continuing the melting for 5min once, continuously introducing the hydrogen-argon mixed gas in the melting process, cooling for 3min, turning the ingot obtained by melting up and down for 180 degrees to obtain a melting period, repeating the 5 melting periods, and fully cooling the alloy to obtain the TiAl alloy containing hydrogen elements.
Wherein, the ventilation mode is as follows: introducing hydrogen and argon mixed gas into a vacuum arc melting furnace is carried out by adopting a plasma-assisted alloying device (as shown in figure 5) which comprisesThe gas mixing system, the smelting system and the exhaust system are sequentially connected, and the gas mixing system comprises a gas mixing tank and an H2、O2、N2Four kinds of gaseous storage steel bottle of Ar, the relief pressure valve is installed in the exit of every gaseous storage steel bottle, and the relief pressure valve passes through the tetrafluoro pipe connection with gas mixing tank, all has concatenated high-pressure stop valve and float flowmeter in proper order on every pipeline, through float flowmeter, high-pressure stop valve and the gaseous flow that gets into the gas mixing tank of relief pressure valve cooperation control hydrogen argon, and the mist reentrants system of smelting after mixing in the gas mixing tank misce bene, after the end of smelting, gets into exhaust system by the outlet duct, exhaust system include exhaust duct, an last installation three way valve of exhaust duct, the vacuum pump is connected to three way valve one end, the gas outlet is connected to. The gas mixing tank is provided with a pressure gauge for measuring the gas pressure in the gas mixing tank.
Putting the raw materials into a water-cooled crucible of a vacuum arc melting furnace, and vacuumizing to a specified vacuum degree. The vacuum state can prevent impurity atoms in the air from reacting with the TiAl alloy and the gas alloying elements at a high temperature, so that the uneven distribution of the alloying elements is avoided, and the metal piece is uniformly heated in the vacuum state, so that the uniform and stable distribution of hydrogen in the TiAl alloy is ensured. And the purity of the hydrogen-argon mixed gas in the smelting process can be improved by washing the gas for 2-3 times, and the hydrogenation treatment of the TiAl alloy is facilitated.
The smelting time is 5min each time in order to ensure that the TiAl alloy raw material is fully melted and hydrogen has sufficient time to be ionized into hydrogen atoms to be diffused into the TiAl alloy under the action of plasma. The TiAl alloy components and H atoms can be uniformly distributed in the alloy to a certain extent by turning up and down. Smelting for 5 times can ensure that the hydrogen absorbed by the TiAl alloy can reach a saturated state.
The hydrogen uptake of the TiAl alloy after the treatment of this example was 0.058 wt.%, which is close to that of the TiAl alloy in a conventional solid-state hydrogen furnace. FIG. 2 shows TiAl alloys before and after hydrogenation treatment at 1100 deg.C for 0.01s-1Stress strain curve under conditions. The rheological resistance is reduced by 32.3 percent, the hot working problem of the TiAl alloy is still the main problem of the current use of the TiAl alloy, and the invention can obviously reduce the resistanceThe deformation resistance of the TiAl alloy is low.
Example 2:
the nitriding process commonly used at present comprises the steps of placing a cylinder body to be treated in a heating furnace, firstly carrying out vacuum-pumping treatment to ensure that the interior of the furnace body is in a vacuum state, then heating to a preset heat preservation temperature, adding methanol into the furnace and controlling the dropping speed of the methanol, simultaneously gradually introducing ammonia gas into the furnace to ensure that the pressure position in the furnace is within a preset pressure range, carrying out heat preservation for a certain time, then cooling, discharging from the furnace and cooling, and thus completing the nitriding treatment on the surface of the cylinder body. In order to detect the hardness of the surface of the nitrided cylinder body, a vickers hardness detection method is adopted as a currently common detection method. However, in the current preparation method, the parameter control of each preparation process is not accurate, so that the nitriding treatment time is longer or the nitriding layer is not uniform, the production cost is increased, and the product percent of pass is reduced.
Based on the above disadvantages, the present embodiment adopts the following method, referring to fig. 3:
the method for alloying the iron-based alloy by the nitrogen comprises the following specific steps:
putting an iron-based metal raw material to be alloyed into a water-cooled crucible of a vacuum arc melting furnace, vacuumizing the vacuum arc melting furnace until the vacuum degree is 1Pa, then washing the vacuum arc melting furnace with nitrogen-argon mixed gas, repeating the gas washing step for 2-3 times, vacuumizing the vacuum arc melting furnace until the vacuum degree is 2Pa, introducing the nitrogen-argon mixed gas into the vacuum arc melting furnace until the melting pressure value is 0.05MPa, the current is 150A, starting melting, continuing for 2min for one time of melting, continuously introducing the nitrogen-argon mixed gas during the melting process, cooling for 3min, turning the ingot obtained by melting up and down by 180 degrees to obtain a melting period, repeating the 3 melting periods, and fully cooling the alloy to obtain the iron-based alloy containing nitrogen elements.
Wherein, the ventilation mode is as follows: the nitrogen-argon mixed gas is introduced into the vacuum arc melting furnace by adopting a plasma auxiliary alloying device (as shown in figure 5), the plasma auxiliary alloying device comprises a gas mixing system, a melting system and an exhaust system which are sequentially connected, and the gas mixing system comprises a gas mixing tank and an H gas mixing tank2、O2、N2Four kinds of gaseous storage steel bottle of Ar, the relief pressure valve is installed in the exit of every gaseous storage steel bottle, and the relief pressure valve passes through the tetrafluoro pipe connection with mixing the gas jar, all has concatenated high pressure stop valve and float flowmeter in proper order on every pipeline, through float flowmeter, high pressure stop valve and the flow of relief pressure valve cooperation control nitrogen argon gas entering mixing the gas jar, and the mist reentrant system of smelting after mixing the gas jar internal mixing, after smelting, gets into exhaust system by the outlet duct, exhaust system include exhaust duct, an last installation three way valve of exhaust duct, the vacuum pump is connected to three way valve one end, the gas outlet is connected to one end. The gas mixing tank is provided with a pressure gauge for measuring the gas pressure in the gas mixing tank.
Putting the iron-based alloy raw material into a water-cooled crucible of a vacuum arc melting furnace, and vacuumizing to a specified vacuum degree. The vacuum state can prevent impurity atoms in the air from reacting with the iron-based alloy and the gas alloying elements at a high temperature, so that the uneven distribution of the alloying elements is avoided, and the metal piece is uniformly heated in the vacuum state, so that the uniform and stable distribution of nitrogen in the iron-based alloy is ensured. The purity of the nitrogen-argon mixed gas in the smelting process can be improved by washing the gas for 2-3 times, and the nitriding treatment of the iron-based alloy is facilitated.
The smelting for 2min each time is to ensure that the iron-based alloy raw material is fully molten, and nitrogen has sufficient time to be ionized into nitrogen atoms to be diffused into the iron-based alloy under the action of plasma. The iron-based alloy components and N atoms can be uniformly distributed in the alloy to a certain extent by turning up and down. Smelting for 3 times can ensure that the nitrogen absorbed by the iron-based alloy can reach a saturated state.
The content of N in the iron-based alloy after the treatment is uniform, and the hardness is obviously improved compared with that before the nitriding treatment.
Example 3:
the invention can add oxygen element into the high-entropy alloy by changing the smelting atmosphere, thereby completing alloying and further improving the alloy performance.
In this embodiment, the method for preparing the high-entropy alloy through the plasma-assisted oxidation treatment by using the following method is provided, referring to fig. 4, and the specific steps are as follows:
putting the needed high-entropy alloy raw material into a water-cooled crucible of a vacuum arc melting furnace, and vacuumizing the vacuum arc melting furnace to the vacuum degree of 5 multiplied by 10-2And Pa, washing the vacuum arc melting furnace with oxygen-argon mixed gas, repeating the gas washing step for 2-3 times, vacuumizing the vacuum arc melting furnace until the vacuum degree is 0.5Pa, introducing the oxygen-argon mixed gas into the vacuum arc melting furnace to reach a melting pressure value of 0.05Mpa and a current value of 300A, starting melting, continuing the melting for 3min, continuously introducing the oxygen-argon mixed gas in the melting process, cooling for 3min, turning the ingot obtained by melting for 180 degrees up and down to obtain a melting period, repeating the melting period for 4 times, and fully cooling the alloy to obtain the high-entropy alloy containing oxygen elements.
Wherein, the ventilation mode is as follows: introducing oxygen-argon mixed gas into a vacuum arc melting furnace is carried out by adopting a plasma auxiliary alloying device (as shown in figure 5), wherein the plasma auxiliary alloying device comprises a gas mixing system, a melting system and an exhaust system which are sequentially connected, and the gas mixing system comprises a gas mixing tank and an H gas mixing tank2、O2、N2Four kinds of gaseous storage steel bottle of Ar, the relief pressure valve is installed in the exit of every gaseous storage steel bottle, and the relief pressure valve passes through the tetrafluoro pipe connection with mixing the gas jar, all has concatenated high pressure stop valve and float flowmeter in proper order on every pipeline, through float flowmeter, high pressure stop valve and the flow of relief pressure valve cooperation control oxygen argon gas entering mixing the gas jar, and the mist reentrant system of smelting after mixing the gas jar internal mixing, after smelting, gets into exhaust system by the outlet duct, exhaust system include exhaust duct, an last installation three way valve of exhaust duct, the vacuum pump is connected to three way valve one end, the gas outlet is connected to one end. The gas mixing tank is provided with a pressure gauge for measuring the gas pressure in the gas mixing tank.
And (3) putting the high-entropy alloy raw material into a water-cooled crucible of a vacuum arc melting furnace, and vacuumizing to a specified vacuum degree. The vacuum state can prevent impurity atoms in the air from reacting with the high-entropy alloy and the gas alloying elements at a high temperature state, so that the uneven distribution of the alloying elements is avoided, and the metal piece is uniformly heated in the vacuum state, so that the uniform and stable distribution of oxygen in the high-entropy alloy is ensured. The purity of oxygen-argon mixed gas in the smelting process can be improved by washing the gas for 2-3 times, and the oxidation treatment of the high-entropy alloy is facilitated.
The purpose of melting for 3min each time is to ensure that the high-entropy alloy raw material is fully melted and oxygen has sufficient time to be ionized into oxygen atoms to be diffused into the high-entropy alloy under the action of plasma. The vertical turnover can ensure that the components of the high-entropy alloy and O atoms are uniformly distributed in the alloy to a certain extent. Smelting for 4 times can ensure that the oxygen absorbed by the high-entropy alloy can reach a saturated state.
The high-entropy alloy treated by the method has uniform oxygen content and improved room-temperature tensile strength. FIG. 6 shows the TiZrHfNbMo alloy before and after the oxygen alloying treatment of this example at room temperature for 0.01s-1Stress strain curve under conditions. It can be found by room temperature compression test (as shown in fig. 6) that the room temperature compressive strength of the material is obviously improved with the oxygen content from 0ppm to 103ppm and finally to 154 ppm.
Example 4:
the technological process of the existing oxygen-nitrogen co-permeation is similar to the nitriding process, a small amount of oxygen is introduced into ammonia gas to realize the oxygen-nitrogen co-permeation, and the method is also suitable for simultaneously alloying oxygen and nitrogen.
In this embodiment, the following method is adopted to prepare the 40Cr alloy through the plasma-assisted oxidative nitridation treatment, and with reference to fig. 7, the specific steps are as follows:
putting the required 40Cr alloy raw material into a water-cooled crucible of a vacuum arc melting furnace, and vacuumizing the vacuum arc melting furnace to the vacuum degree of 5 multiplied by 10-2Pa, washing the vacuum arc melting furnace with oxygen-nitrogen-argon mixed gas, repeating the washing step for 2-3 times, vacuumizing the vacuum arc melting furnace until the vacuum degree is 0.5Pa, introducing the oxygen-nitrogen-argon mixed gas into the vacuum arc melting furnace until the melting pressure value is 0.05Mpa and the current value is 300A, starting melting, continuing to smelt for 3min for one time, continuously introducing the oxygen-argon mixed gas during the melting process, cooling for 3min, and turning the ingot obtained by melting up and down for 180 degrees to obtain the ingotRepeating 4 smelting cycles in one smelting cycle, and fully cooling the alloy to obtain the oxygen-nitrogen element-containing 40Cr alloy.
And (3) putting the 40Cr alloy raw material into a water-cooled crucible of a vacuum arc melting furnace, and vacuumizing to a specified vacuum degree. The vacuum state can prevent impurity atoms in the air from reacting with the 40Cr alloy and the gas alloying elements at a high temperature, so that the uneven distribution of the alloying elements is avoided, and the metal piece is uniformly heated in the vacuum state, so that the uniform and stable distribution of oxygen in the 40Cr alloy is ensured. The purity of the oxygen-nitrogen-argon mixed gas in the smelting process can be improved by washing the gas for 2-3 times, and the oxynitridation treatment of the 40Cr alloy is facilitated.
The reason for melting for 3min each time is to ensure that the 40Cr alloy raw material is fully melted and oxygen has enough time to be ionized into oxygen atoms and nitrogen atoms to be diffused into the 40Cr alloy under the action of plasma. The up-down turning can ensure that the 40Cr alloy composition and O, N atoms are uniformly distributed in the alloy to a certain extent. Smelting for 4 times can ensure that oxygen and nitrogen absorbed by the 40Cr alloy can reach a saturated state.
The content of oxygen and nitrogen in the 40Cr treated by the method is uniformly distributed, and the alloy hardness is improved to 60 HRC.
Example 5:
the hydrogenation treatment commonly used for the titanium alloy at present comprises the steps of placing an alloy mother ingot to be treated in a vacuum furnace, firstly carrying out vacuum-pumping treatment to ensure that the interior of a furnace body is in a vacuum state, then heating to a preset heat preservation temperature, adding hydrogen and argon mixed gas into the furnace, and achieving the hydrogenation treatment of the alloy by controlling the pressure, the temperature and the flow rate of the mixed gas. However, the prior hydrogenation treatment process needs matched equipment, so that the production cost is greatly increased, and meanwhile, the manufacturing process of the mother ingot and the hydrogenation treatment are two parts, so that the hydrogenation treatment period is greatly increased.
Based on the above disadvantages, the present embodiment adopts the following method, with reference to fig. 8:
the method for alloying the titanium alloy by hydrogen comprises the following specific steps:
putting Ti alloy raw material to be alloyed into a water-cooled crucible of a vacuum arc melting furnace, and vacuumizing the vacuum arc melting furnaceTo a vacuum of 5 × 10-3And Pa, washing the vacuum arc melting furnace with a small amount of hydrogen-argon mixed gas, repeating the gas washing step for 2-3 times, vacuumizing the vacuum arc melting furnace until the vacuum degree is 0.5Pa, introducing the hydrogen-argon mixed gas into the vacuum arc melting furnace until the melting pressure value is 0.05Mpa and the current is 250A, starting melting, continuing the melting for 5min for one time, continuously introducing the hydrogen-argon mixed gas in the melting process, cooling for 3min, turning the ingot obtained by melting for 180 degrees up and down to obtain a melting period, repeating the 5 melting periods, and fully cooling the alloy to obtain the Ti alloy containing hydrogen elements.
Wherein, the ventilation mode is as follows: introducing hydrogen and argon mixed gas into a vacuum arc melting furnace is carried out by adopting a plasma auxiliary alloying device (as shown in figure 5), wherein the plasma auxiliary alloying device comprises a gas mixing system, a melting system and an exhaust system which are sequentially connected, and the gas mixing system comprises a gas mixing tank and an H gas mixing tank2、O2、N2Four kinds of gaseous storage steel bottle of Ar, the relief pressure valve is installed in the exit of every gaseous storage steel bottle, and the relief pressure valve passes through the tetrafluoro pipe connection with gas mixing tank, all has concatenated high-pressure stop valve and float flowmeter in proper order on every pipeline, through float flowmeter, high-pressure stop valve and the gaseous flow that gets into the gas mixing tank of relief pressure valve cooperation control hydrogen argon, and the mist reentrants system of smelting after mixing in the gas mixing tank misce bene, after the end of smelting, gets into exhaust system by the outlet duct, exhaust system include exhaust duct, an last installation three way valve of exhaust duct, the vacuum pump is connected to three way valve one end, the gas outlet is connected to. The gas mixing tank is provided with a pressure gauge for measuring the gas pressure in the gas mixing tank.
Putting the raw materials into a water-cooled crucible of a vacuum arc melting furnace, and vacuumizing to a specified vacuum degree. The vacuum state can prevent impurity atoms in the air from reacting with the Ti alloy and the gas alloying elements at a high temperature, so that the uneven distribution of the alloying elements is avoided, and the metal piece is uniformly heated in the vacuum state, so that the uniform and stable distribution of hydrogen in the Ti alloy is ensured. The purity of the hydrogen-argon mixed gas in the smelting process can be improved by washing the gas for 2-3 times, and the hydrogenation treatment of the Ti alloy is facilitated.
The smelting time is 5min each time in order to ensure that the Ti alloy raw material is fully melted and hydrogen has enough time to be ionized into hydrogen atoms to be diffused into the Ti alloy under the action of plasma. The vertical turning can ensure that the Ti alloy components and H atoms are uniformly distributed in the alloy to a certain extent. Smelting for 5 times can ensure that the hydrogen absorbed by the Ti alloy can reach a saturated state.
The hydrogen absorption amount of the Ti alloy after the treatment of the example was 350ppm, which is close to the hydrogen absorption amount of the Ti alloy in the conventional solid-state hydrogen furnace. FIG. 9 shows Ti alloys before and after hydrotreating at 850 deg.C for 0.01s-1Stress strain curve under conditions. The rheological resistance of the Ti alloy is obviously reduced, the hot processing problem of the Ti alloy is still the main problem of the existing Ti alloy, and the deformation resistance of the Ti alloy can be obviously reduced by the invention.
Example 6:
the conventional hydrogenation treatment of zirconium alloy comprises the steps of placing an alloy mother ingot to be treated in a vacuum furnace, firstly carrying out vacuum-pumping treatment to ensure that the interior of the furnace body is in a vacuum state, then heating to a preset heat preservation temperature, adding hydrogen and argon mixed gas into the furnace, and achieving hydrogenation treatment of the alloy by controlling pressure, temperature and mixed gas flow rate. However, the prior hydrogenation treatment process needs matched equipment, so that the production cost is greatly increased, and meanwhile, the manufacturing process of the mother ingot and the hydrogenation treatment are two parts, so that the hydrogenation treatment period is greatly increased.
Based on the above disadvantages, the present embodiment adopts the following method, referring to fig. 10:
the method for alloying the zirconium alloy by hydrogen comprises the following specific steps:
putting Zr alloy raw material to be alloyed into a water-cooled crucible of a vacuum arc melting furnace, and vacuumizing the vacuum arc melting furnace to the vacuum degree of 5 multiplied by 10-3Pa, washing the vacuum arc melting furnace with a small amount of hydrogen-argon mixed gas, repeating the washing step for 2-3 times, vacuumizing the vacuum arc melting furnace to the vacuum degree of 0.5Pa, introducing the hydrogen-argon mixed gas into the vacuum arc melting furnace to the melting pressure of 0.05Mpa and the current of 350A, starting melting, continuing the melting for one time for 2min, and continuously introducing the hydrogen-argon mixed gas into the melting processAnd cooling the mixed gas for 3min, turning the ingot obtained by smelting up and down by 180 degrees to obtain a smelting period, repeating the smelting period for 4 times, and fully cooling the alloy to obtain the Zr alloy containing the hydrogen element.
Wherein, the ventilation mode is as follows: introducing hydrogen and argon mixed gas into a vacuum arc melting furnace is carried out by adopting a plasma auxiliary alloying device (as shown in figure 5), wherein the plasma auxiliary alloying device comprises a gas mixing system, a melting system and an exhaust system which are sequentially connected, and the gas mixing system comprises a gas mixing tank and an H gas mixing tank2、O2、N2Four kinds of gaseous storage steel bottle of Ar, the relief pressure valve is installed in the exit of every gaseous storage steel bottle, and the relief pressure valve passes through the tetrafluoro pipe connection with gas mixing tank, all has concatenated high-pressure stop valve and float flowmeter in proper order on every pipeline, through float flowmeter, high-pressure stop valve and the gaseous flow that gets into the gas mixing tank of relief pressure valve cooperation control hydrogen argon, and the mist reentrants system of smelting after mixing in the gas mixing tank misce bene, after the end of smelting, gets into exhaust system by the outlet duct, exhaust system include exhaust duct, an last installation three way valve of exhaust duct, the vacuum pump is connected to three way valve one end, the gas outlet is connected to. The gas mixing tank is provided with a pressure gauge for measuring the gas pressure in the gas mixing tank.
Putting the raw materials into a water-cooled crucible of a vacuum arc melting furnace, and vacuumizing to a specified vacuum degree. The vacuum state can prevent impurity atoms in the air from reacting with the Zr alloy and gas alloying elements at a high temperature state, so that the uneven distribution of the alloying elements is avoided, and the metal piece is uniformly heated in the vacuum state, so that the uniform and stable distribution of hydrogen in the Zr alloy is ensured. The purity of the hydrogen-argon mixed gas in the smelting process can be improved by washing the gas for 2-3 times, and the hydrogenation treatment of the Zr alloy is facilitated.
The smelting for 2min each time is to ensure that the Zr alloy raw material is fully molten, and hydrogen has enough time to be ionized into hydrogen atoms to be diffused into the Zr alloy under the action of plasma. The up-and-down turning can ensure that Zr alloy components and H atoms are uniformly distributed in the alloy to a certain extent. Smelting for 4 times can ensure that the hydrogen absorbed by the Zr alloy can reach a saturated state.
The hydrogen absorption amount of the Zr alloy after the treatment of this example was 5.19 at.%, which is close to the hydrogen absorption amount of the Zr alloy in the conventional solid-state hydrogen furnace. FIG. 11 shows Zr alloy at 700 ℃ for 0.01s before and after hydrotreating-1The rheological resistance of the stress-strain curve under the condition is obviously reduced.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and all simple modifications and equivalent variations of the above embodiment according to the present invention are within the scope of the present invention.
Claims (8)
1. A method of plasma assisted gas alloying comprising the steps of:
putting a metal raw material to be alloyed into a water-cooled crucible of a vacuum arc melting furnace, vacuumizing the vacuum arc melting furnace, washing the vacuum arc melting furnace with mixed gas, repeating the gas washing step for 2-3 times, vacuumizing the vacuum arc melting furnace, introducing the mixed gas into the vacuum arc melting furnace to reach a melting pressure value, starting melting, continuing the melting for 2-5 min for one time, continuously introducing the mixed gas during the melting process, cooling for 3min, turning the ingot obtained by melting for 180 degrees up and down to obtain a melting period, repeating the melting period for 3-5 times, and fully cooling the alloy to obtain the alloyed metal containing gas elements.
2. The plasma-assisted gas alloying method according to claim 1, wherein the metallic material to be alloyed comprises any one of a titanium alloy, a zirconium alloy, a titanium-aluminum alloy, an iron-based alloy, and a high-entropy alloy.
3. The method of plasma-assisted gas alloying according to claim 1,
the vacuum degree of the vacuum arc melting furnace for vacuum pumping is 5 multiplied by 10-3Pa～2Pa。
4. According to claim 1The plasma-assisted gas alloying method is characterized in that the mixed gas is X2/Ar2Wherein X is H, O, N.
5. The plasma-assisted gas alloying method as claimed in claim 1, wherein the introduction of the mixed gas into the vacuum arc melting furnace is performed by using a plasma-assisted alloying device, the plasma-assisted alloying device comprises a gas mixing system, a melting system and an exhaust system which are connected in sequence, and the gas mixing system comprises a gas mixing tank and an H gas mixing tank2、O2、N2The steel bottle is stored to four kinds of gases of Ar, and the exit of every gas storage steel bottle is installed the relief pressure valve, relief pressure valve and gas mixing tank pass through the tetrafluoro pipe connection, all have concatenated high-pressure stop valve and float flowmeter in proper order on every pipeline, through float flowmeter, high-pressure stop valve and the four kinds of gaseous flow that get into the gas mixing tank of relief pressure valve cooperation control, the mist gets into the system of smelting again after mixing the gas tank internal misce bene, after smelting, gets into exhaust system by the outlet duct, exhaust system include exhaust duct, exhaust duct on install a three way valve, three way valve one end connect the vacuum pump, the gas outlet is connected to one end.
6. The plasma-assisted gas alloying method according to claim 5, wherein the gas mixing tank is provided with a pressure gauge for measuring the gas pressure in the gas mixing tank.
7. The plasma-assisted gas alloying method of claim 1 wherein the melt pressure is 0.05 Mpa.
8. The plasma-assisted gas alloying method according to claim 1, wherein the current during the smelting process is 150-400A.
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