CN114561594A - Corrosion-resistant high-ductility composite alloy for manufacturing new energy battery - Google Patents
Corrosion-resistant high-ductility composite alloy for manufacturing new energy battery Download PDFInfo
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- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/26—Methods of annealing
- C21D1/28—Normalising
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- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
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- C23C24/00—Coating starting from inorganic powder
- C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
- C23C24/10—Coating starting from inorganic powder by application of heat or pressure and heat with intermediate formation of a liquid phase in the layer
- C23C24/103—Coating with metallic material, i.e. metals or metal alloys, optionally comprising hard particles, e.g. oxides, carbides or nitrides
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- B22F9/00—Making metallic powder or suspensions thereof
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Abstract
The invention discloses a corrosion-resistant high-ductility composite alloy for manufacturing a new energy battery, which comprises the following components in percentage by mass: 0.02-0.06% of C, 0.38-0.86% of Mn, 0.01-0.03% of B, Ti: 0.53-0.81%, Ni: 0.21-0.45%, Cr: 5-9.8%, As: 0.11-0.15%, V: 0.7-1.0%, Re 0.2-0.5%, Mg: 0.01 to 0.038%, Zr: 0.01-0.015%, Cu: 0.01-0.03%, Rh: 0.01-0.035%, PT is less than or equal to 0.028%, PD is less than or equal to 0.033%, and the balance is Fe and inevitable impurities; the invention has high hardness, and simultaneously has excellent impact strength, heat resistance, wear resistance and corrosion resistance.
Description
Technical Field
The invention belongs to the technical field of new energy alloy materials, and particularly relates to a corrosion-resistant high-ductility composite alloy for manufacturing a new energy battery.
Background
The structure of a solar cell or a bracket of a water heater is well known, and most of the solar cell or the bracket is made of aluminum alloy due to excellent strength and strength-to-weight ratio of the aluminum alloy. The processing method of the aluminum alloy bracket is also known, for example, the invention is similar to the structure and the processing technology of the bracket of other solar cells or water heaters in the market, in the actual use process, although the aluminum profile can be protected to a certain extent by forming an oxide film on the surface, the aluminum profile can be oxidized and corroded after being used for a long time or in a humid environment, especially, after the oxide layer is damaged by a hard object, the exposed part of the aluminum profile can be seriously corroded and can become a corrosion stress concentration point, the quality and the service life of the device are seriously influenced, and huge loss is caused to social resources; therefore, there is a need for a corrosion-resistant high-ductility composite alloy for new energy battery manufacturing to at least partially solve the problems of the prior art; the inventors of the present invention have made extensive studies on the above problems, and have made the present invention.
Disclosure of Invention
The invention mainly solves the technical problem of providing a corrosion-resistant high-ductility composite alloy for manufacturing new energy batteries, which has high hardness and simultaneously has excellent impact strength, heat resistance, wear resistance and corrosion resistance.
In order to solve the technical problems, the invention adopts a technical scheme that: a corrosion-resistant high-ductility composite alloy for manufacturing a new energy battery comprises the following components in percentage by mass: 0.02-0.06% of C, 0.38-0.86% of Mn, 0.01-0.03% of B, Ti: 0.53-0.81%, Ni: 0.21-0.45%, Cr: 5-9.8%, As: 0.11-0.15%, V: 0.7-1.0%, Re 0.2-0.5%, Mg: 0.01 to 0.038%, Zr: 0.01-0.015%, Cu: 0.01-0.03%, Rh: 0.01-0.035%, PT is less than or equal to 0.028%, PD is less than or equal to 0.033%, and the balance is Fe and inevitable impurities;
the method for preparing the composite alloy comprises the following steps:
s1, smelting: adding scrap steel into a medium-frequency induction smelting furnace, heating to 1500-;
s2, heat treatment: normalizing, quenching and high-temperature tempering the obtained blank in sequence; in the normalizing treatment, the temperature is raised to 980-1030 ℃, the temperature is kept for 50-80min, and the air is cooled to the room temperature; in the quenching treatment, the temperature is raised to 800-820 ℃, the temperature is kept for 30-75min, and the water is cooled to the room temperature; in the high-temperature tempering treatment, the temperature is increased to 530 ℃ for 500-;
s3, preprocessing: polishing the heat-treated composite alloy obtained in the step S2 by using sand paper, and cleaning by using acetone and ethanol to obtain a composite alloy; putting 15-35 parts of titanium powder and 20-35 parts of graphite powder into a ball mill, uniformly mixing to obtain cladding powder, mixing the cladding powder and an adhesive into paste, uniformly coating the paste on the surface of the obtained composite alloy, wherein the thickness of the paste is 1-3mm, then putting the paste into an electric furnace, setting the temperature of the electric furnace at 160-180 ℃, preserving heat for 2-3.5h, and cooling the paste to room temperature along with the furnace to obtain a pretreatment ball; the titanium powder comprises the following components in percentage by mass: 0.1-0.15% of C, As: 0.2-0.8%, Ti: 0.6-1.8%, Fe: 0.2-0.3%, Pb: 0.02-0.06%, N: 0.02-0.08%, O: 0.1-0.55%, H: 0.01-0.03 percent of Ti, and the balance of Ti;
s4, reacting nitrogen arc cladding: putting the pretreated ball obtained in the step S3 into a reaction nitrogen arc cladding system for reaction nitrogen arc cladding to obtain a composite alloy, wherein the reaction nitrogen arc cladding system adopts an argon arc welding machine, tungsten with a high melting point is used as a cathode, the pretreated ball is used as an anode, and nitrogen is used as a protective gas and a reaction gas; the parameters of the reaction nitrogen arc cladding process are as follows: cladding current 150-.
Further, the components of the material comprise the following components in percentage by mass: 0.045% of C, 0.73% of Mn, 0.02% of B, Ti: 0.53%, Ni: 0.35%, Cr: 8.6%, As: 0.14%, V: 0.75%, Re: 0.33%, Mg: 0.025%, Zr: 0.014%, Cu: 0.025%, Rh: 0.026%, PT: 0.019%, PD: 0.03%, and the balance of Fe and inevitable impurities.
Further, in S3, the binder is a sodium carboxymethyl cellulose solution or water glass.
Further, in S1, adding scrap steel into a medium-frequency induction smelting furnace, heating to 1513 ℃, keeping the temperature for 25min, adding ferrovanadium, adding ferrosilicon and ferromanganese after the scrap steel is completely melted, heating to 1545 ℃ until the scrap steel is completely melted, adding nickel alloy, calcium silicon alloy and ferrozirconium, completely melting all raw materials to obtain molten steel, pouring, opening the mold after the molten steel is completely solidified, and cooling the furnace to room temperature to obtain a blank; the pouring and die sinking after the molten steel is completely solidified comprises the following steps: manufacturing a casting blank forming die, a molten steel collector and a molten steel flow opening valve body, wherein the casting blank forming die is a universal blank forming die, the molten steel collector is structurally a graphite crucible and is provided with a bottom opening, the bottom opening is internally provided with a molten steel flow opening valve body, and the molten steel flow opening valve body is adaptive to block the bottom opening in an initial state; one end of the molten steel flow channel is communicated with the valve body position of the molten steel flow outlet at the bottom of the molten steel collector; molten steel in the medium-frequency induction smelting furnace is filled into the molten steel collector, the valve body of the molten steel circulation port is opened, molten steel with slag at the bottom of the molten steel collector flows into the molten steel flow channel, a machine vision detector is arranged at the outlet of the molten steel flow channel, and the valve body of the molten steel circulation port is closed when the content of the slag in the molten steel is detected to be reduced to a set steel slag content limit detection standard; the edge of the molten steel collector is connected with a plurality of collector supports, the collector supports are provided with a mold approach sensor, and when the mold approach sensor senses that a casting blank forming mold approaches, the controller controls the molten steel collector to be in a suspension state, so that one side of the molten steel collector, which is sensed by the mold approach sensor to approach the casting blank forming mold, inclines downwards; enabling slag-removed molten steel at the upper part of the molten steel collector to flow out of a casting blank forming die through one side of the molten steel collector; the lower molten steel with slag flows into a molten steel collector with slag through the molten steel flow channel; the bottom of the casting blank forming die is provided with a pressure sensor, and after the pressure sensor detects that the molten steel injected into the casting blank forming die reaches the specified weight, the new casting blank forming die is replaced to continue to inject the molten steel; and opening the mold after the molten steel is completely solidified.
Further, in S2, in the normalizing treatment, the temperature is raised to 1015 ℃, the temperature is maintained for 55min, and the air is cooled to the room temperature; in the quenching treatment, the temperature is raised to 805 ℃, the temperature is kept for 74min, and the water is cooled to the room temperature; in the high-temperature tempering treatment, the temperature is raised to 505 ℃, the temperature is kept for 145min, and the water is cooled to the room temperature, so that the heat-treated composite alloy is obtained.
Further, in S2, in the normalizing process, the temperature rise rate decreases with the temperature rise in the course of raising the temperature to 980-1030 ℃; the decreasing rate of temperature rise with increasing temperature comprises: the blank space placement and the heating of the space where the blank to be heated is located are carried out through an electric heating wire heating support plate, a heat insulation radiation-proof plate, a blank heat-insulation cover and a temperature-resistant fan, and the heated blank is uniformly heated, wherein two ends of the electric heating wire heating support plate are respectively connected with a heating negative electrode and a heating positive electrode; the heating wire heating supporting plate is provided with a plurality of heat insulation supporting points, a heat insulation radiation-proof plate is horizontally placed on the heat insulation supporting points, the contact surface of the heat insulation radiation-proof plate and the heat insulation supporting points is flat, the other side of the heat insulation radiation-proof plate is provided with a plurality of blank bottom space supporting points, the number of the heat insulation supporting points and the number of the blank bottom space supporting points are not less than 3, the heat insulation supporting points and the blank bottom space supporting points are used for isolating single-side heating heat conduction and heat radiation of the bottom of a blank, and supporting and stable placement for comprehensively and uniformly heating and heating the blank in a located space are provided; the blank heat-insulating cover is fixedly covered on the upper end of the heating wire heating supporting plate; the bottom end of the heating wire heating supporting plate and the blank heat-insulating cover body are provided with a plurality of temperature detection probes for detecting the heating temperature of the blank;
the blank heat-insulating cover is divided into an upper part and a lower part, the lower part is provided with an opening to cover the heating wire heating supporting plate, and the upper part is provided with a temperature-resistant fan which is used for uniformly distributing heat in an airflow accelerating flowing space in the blank heat-insulating cover; the heating negative electrode and the heating positive electrode are respectively connected with the positive electrode and the negative electrode of the power supply; when the heating negative electrode and the heating positive electrode are electrified, the heating wire heating supporting plate is electrically heated, the heat insulation radiation-proof plate arranged on the heat insulation fulcrum of the heating wire heating supporting plate isolates the direct heating and the non-uniform heat radiation of the bottom, and meanwhile, the heat-resistant fan rotates to accelerate the airflow in the blank heat-insulation cover to flow so as to uniformly heat the blank;
when the blank is heated, the temperature detection probe detects the temperature of a heating space in the blank heat-insulating cover in real time, the actual temperature of the blank is calculated according to the temperature of the heating space and the heat conduction characteristic of the blank, the temperature detection probe feeds a detected temperature signal back to the control operation system, the control operation system performs control calculation according to a set temperature-rising program, and then the currents of a heating negative electrode and a heating positive electrode on two sides of a heating-up supporting plate of an electric heating wire are adjusted, the rotating speed of a temperature-resistant fan is adjusted, and the temperature-rising rate is reduced along with the rise of the temperature.
Further, in S2, in the quenching treatment, the temperature is increased to 800-820 ℃, the temperature is kept for 30-75min, and the cooling speed is reduced along with the reduction of the temperature in the process of water cooling to the room temperature.
Further, in S3, the titanium powder includes, by mass: 0.13% of C, As: 0.55%, Ti: 1.3%, Fe: 0.25%, Pb: 0.029%, N: 0.046%, O: 0.1%, H: 0.01 percent, and the balance of Ti.
In S3, 20 parts of titanium powder and 30 parts of graphite powder are put into a ball mill to be uniformly mixed to obtain cladding powder, the cladding powder and an adhesive are mixed into paste to be uniformly coated on the surface of the obtained composite alloy, the thickness of the cladding powder is 2mm, the cladding powder and the adhesive are put into an electric furnace, the temperature of the electric furnace is set to be 170 ℃, the heat is preserved for 3 hours, and the pretreatment ball is obtained after the cladding powder and the adhesive are cooled to room temperature along with the furnace.
Further, in S4, the parameters of the reactive nitrogen arc cladding process are specifically as follows: cladding current 175A, nitrogen flow 14L/min.
The invention has the beneficial effects that:
in the heat treatment process of the composite alloy, the normalizing treatment is firstly carried out, crystal grains are refined, the structure is homogenized, the dendritic structure and the overheated structure are eliminated, the internal stress of the composite alloy is removed, and the hardness of the material is increased; then, a quenching process is carried out, in the cooling process of quenching, rapid cooling is carried out in the range of the most unstable supercooled austenite in the cooling initial stage, and then the reduced cooling rate is adopted to ensure that the martensite is obtained and simultaneously reduce the internal stress in the composite alloy to prevent deformation and cracking; in the blank forming process, the impurity content of the blank is lower through liquid-slag level separation; in the heating process, the material is heated more uniformly in the heating process and the temperature is controlled more accurately by uniform space heating and real-time heating control, so that the material performance is further improved; and after quenching, high-temperature tempering is carried out, so that residual stress generated during quenching of the composite alloy is eliminated, brittleness is reduced, toughness is improved, deformation and cracking are prevented, and the composite alloy with excellent comprehensive performance is obtained.
Detailed Description
The following detailed description of the preferred embodiments of the present invention is provided to enable those skilled in the art to more readily understand the advantages and features of the present invention and to clearly and clearly define the scope of the present invention.
Example 1
The composite alloy comprises the following components in percentage by mass: 0.02% of C, 0.44% of Mn, 0.03% of B, Ti: 0.64%, Ni: 0.45%, Cr: 8.3%, As: 0.11%, V: 0.9%, Re: 0.2%, Mg: 0.018%, Zr: 0.015%, Cu: 0.01%, Rh: 0.035%, PT: 0.028%, PD: 0.033%, the balance being Fe and unavoidable impurities.
The preparation method of the composite alloy comprises the following steps:
s1, smelting: adding scrap steel into a medium-frequency induction smelting furnace, heating to 1502 ℃, preserving heat for 40min, adding ferrovanadium, adding ferrosilicon and ferromanganese after complete melting, heating to 1570 ℃ until complete melting, adding nickel alloy, silicon-calcium alloy and ferrozirconium, completely melting all raw materials, slagging off to obtain molten steel, pouring, opening the mold after the molten steel is completely solidified, and cooling the furnace to room temperature to obtain a blank;
s2, heat treatment: normalizing, quenching and high-temperature tempering the obtained blank in sequence; in the normalizing treatment, the temperature is raised to 1030 ℃, the temperature is kept for 50min, and the air is cooled to the room temperature; in the quenching treatment, the temperature is raised to 820 ℃, the temperature is kept for 30min, and the water is cooled to the room temperature; in the high-temperature tempering treatment, the temperature is increased to 509 ℃, the temperature is kept for 142min, and water is cooled to the room temperature, so that the heat-treated composite alloy is obtained;
s3, preprocessing: polishing the heat-treated composite alloy obtained in the step S2 for 36min by using sand paper, cleaning by using acetone and then cleaning by using ethanol to obtain a composite alloy; putting 35 parts of titanium powder and 22 parts of graphite powder into a ball mill, uniformly mixing to obtain cladding powder, mixing the cladding powder and an adhesive into paste, uniformly coating the paste on the surface of the obtained composite alloy, wherein the thickness of the paste is 1mm, then putting the paste into an electric furnace, setting the temperature of the electric furnace to 160 ℃, keeping the temperature for 3.5 hours, and cooling the paste to room temperature along with the furnace to obtain a pretreatment ball; the titanium powder comprises the following components in percentage by mass: 0.1% of C, As: 0.4%, Ti: 1.8%, Fe: 0.25%, Pb: 0.06%, N: 0.08%, O: 0.1%, H: 0.019 percent, and the balance of Ti;
s4, reacting nitrogen arc cladding: putting the pretreated ball obtained in the step S3 into a reaction nitrogen arc cladding system for reaction nitrogen arc cladding to obtain a composite alloy, wherein the reaction nitrogen arc cladding system adopts an argon arc welding machine, tungsten with a high melting point is used as a cathode, the pretreated ball is used as an anode, and nitrogen is used as a protective gas and a reaction gas; the parameters of the reaction nitrogen arc cladding process are as follows: cladding current 150A and nitrogen flow rate 14L/min.
Example 2
The composite alloy comprises the following components in percentage by mass: 0.06% of C, 0.38% of Mn, 0.022% of B, Ti: 0.81%, Ni: 0.38%, Cr: 5%, As: 0.13%, V: 1.0%, Re: 0.45%, Mg: 0.01%, Zr: 0.014%, Cu: 0.03%, Rh: 0.01%, PT: 0.02%, PD: 0.03%, and the balance of Fe and inevitable impurities.
The preparation method of the composite alloy comprises the following steps:
s1, smelting: adding scrap steel into a medium-frequency induction smelting furnace, heating to 1520 ℃, preserving heat for 20min, adding ferrovanadium, adding ferrosilicon and ferromanganese after complete melting, heating to 1540 ℃, adding nickel alloy, silicon-calcium alloy and ferrozirconium after complete melting, completely melting all raw materials, slagging off to obtain molten steel, pouring, opening the mold after the molten steel is completely solidified, and cooling the furnace to room temperature to obtain a blank;
s2, heat treatment: normalizing, quenching and high-temperature tempering the obtained blank in sequence; in the normalizing treatment, the temperature is raised to 1005 ℃, the temperature is kept for 75min, and the air is cooled to the room temperature; in the quenching treatment, the temperature is raised to 800 ℃, the temperature is kept for 75min, and the water is cooled to the room temperature; in the high-temperature tempering treatment, the temperature is raised to 500 ℃, the temperature is kept for 150min, and water is cooled to the room temperature, so that the heat-treated composite alloy is obtained; in the normalizing treatment, in the process of raising the temperature to 1005 ℃, the temperature raising rate is reduced along with the temperature rise, and the average temperature raising rate is 8 ℃/min; in the quenching treatment, the temperature is raised to 800 ℃, the temperature is kept for 75min, and the cooling speed is reduced along with the reduction of the temperature in the process of water cooling to room temperature;
s3, pretreatment: polishing the heat-treated composite alloy obtained in the step S2 for 50min by using sand paper, cleaning by using acetone and then cleaning by using ethanol to obtain a composite alloy; putting 20 parts of titanium powder and 20 parts of graphite powder into a ball mill, uniformly mixing to obtain cladding powder, mixing the cladding powder with water glass into paste, uniformly coating the paste on the surface of the obtained composite alloy, wherein the thickness of the paste is 3mm, then putting the paste into an electric furnace, setting the temperature of the electric furnace to be 173 ℃, preserving the heat for 3 hours, and cooling the paste to room temperature along with the furnace to obtain a pretreatment ball; the titanium powder comprises the following components in percentage by mass: 0.14% of C, As: 0.8%, Ti: 1.2%, Fe: 0.2%, Pb: 0.02%, N: 0.029%, O: 0.45%, H: 0.01 percent, and the balance of Ti;
s4, reacting nitrogen arc cladding: putting the pretreated ball obtained in the step S3 into a reaction nitrogen arc cladding system for reaction nitrogen arc cladding to obtain a composite alloy, wherein the reaction nitrogen arc cladding system adopts an argon arc welding machine, tungsten with a high melting point is used as a cathode, the pretreated ball is used as an anode, and nitrogen is used as a protective gas and a reaction gas; the parameters of the reaction nitrogen arc cladding process are as follows: cladding current 159A, nitrogen flow 18L/min.
Example 3
The composite alloy comprises the following components in percentage by mass: 0.05% of C, 0.86% of Mn, 0.01% of B, Ti: 0.53%, Ni: 0.21%, Cr: 9.8%, As: 0.15%, V: 0.7%, Re 0.5%, Mg: 0.038%, Zr: 0.015%, Cu: 0.018%, Rh: 0.019%, PT: 0.021%, PD: 0.029%, and the balance of Fe and unavoidable impurities.
The preparation method of the composite alloy comprises the following steps:
s1, smelting: adding scrap steel into a medium-frequency induction smelting furnace, heating to 1500 ℃, keeping the temperature for 45min, adding ferrovanadium, adding ferrosilicon and ferromanganese after complete melting, heating to 1530 ℃, heating to complete melting, adding nickel alloy, silicon-calcium alloy and ferrozirconium, completely melting all raw materials, slagging off to obtain molten steel, pouring, opening the mold after the molten steel is completely solidified, and cooling the furnace to room temperature to obtain a blank;
s2, heat treatment: normalizing, quenching and high-temperature tempering the obtained blank in sequence; in the normalizing treatment, the temperature is raised to 980 ℃, the temperature is kept for 80min, and the air is cooled to the room temperature; in the quenching treatment, the temperature is raised to 804 ℃, the temperature is kept for 70min, and the water is cooled to the room temperature; in the high-temperature tempering treatment, the temperature is increased to 530 ℃, the temperature is kept for 130min, and the water is cooled to the room temperature, so that the heat-treated composite alloy is obtained; in the normalizing treatment, in the process of raising the temperature to 980 ℃, the temperature rise rate is reduced along with the rise of the temperature, and the average temperature rise rate is 5 ℃/min; in the quenching treatment, the temperature is raised to 804 ℃, the temperature is kept for 70min, and the cooling speed is reduced along with the reduction of the temperature in the process of water cooling to room temperature;
s3, preprocessing: polishing the heat-treated composite alloy obtained in the step S2 for 20min by using sand paper, cleaning by using acetone and then cleaning by using ethanol to obtain a composite alloy; putting 35 parts of titanium powder and 35 parts of graphite powder into a ball mill, uniformly mixing to obtain cladding powder, mixing the cladding powder with ethanol to obtain paste, uniformly coating the paste on the surface of the obtained composite alloy, wherein the thickness of the paste is 2mm, then putting the paste into an electric furnace, setting the temperature of the electric furnace to be 180 ℃, preserving the heat for 2 hours, and cooling the paste to room temperature along with the furnace to obtain a pretreated ball; the titanium powder comprises the following components in percentage by mass: 0.15% of C, As: 0.2%, Ti: 0.6%, Fe: 0.3%, Pb: 0.05%, N: 0.02%, O: 0.55%, H: 0.03 percent, and the balance being Ti;
s4, reacting nitrogen arc cladding: putting the pretreated ball obtained in the step S3 into a reaction nitrogen arc cladding system for reaction nitrogen arc cladding to obtain a composite alloy, wherein the reaction nitrogen arc cladding system adopts an argon arc welding machine, tungsten with a high melting point is used as a cathode, the pretreated ball is used as an anode, and nitrogen is used as a protective gas and a reaction gas; the parameters of the reaction nitrogen arc cladding process are as follows: cladding current 180A and nitrogen flow rate 12L/min.
Example 4
The composite alloy comprises the following components in percentage by mass: 0.045% of C, 0.73% of Mn, 0.02% of B, Ti: 0.53%, Ni: 0.35%, Cr: 8.6%, As: 0.14%, V: 0.75%, Re: 0.33%, Mg: 0.025%, Zr: 0.014%, Cu: 0.025%, Rh: 0.026%, PT: 0.019%, PD: 0.03%, and the balance of Fe and inevitable impurities.
The preparation method of the composite alloy comprises the following steps:
s1, smelting: adding scrap steel into a medium-frequency induction smelting furnace, heating to 1513 ℃, preserving heat for 25min, adding ferrovanadium, adding ferrosilicon and ferromanganese after complete melting, heating to 1545 ℃ until complete melting, adding nickel alloy, silicon-calcium alloy and ferrozirconium, completely melting all raw materials, slagging off to obtain molten steel, pouring, opening the mold after the molten steel is completely solidified, and cooling the furnace to room temperature to obtain a blank;
s2, heat treatment: normalizing, quenching and high-temperature tempering the obtained blank in sequence; in the normalizing treatment, the temperature is increased to 1015 ℃, the temperature is kept for 55min, and the air is cooled to the room temperature; in the quenching treatment, the temperature is raised to 805 ℃, the temperature is kept for 74min, and the water is cooled to the room temperature; in the high-temperature tempering treatment, the temperature is raised to 505 ℃, the temperature is kept for 145min, and the water is cooled to the room temperature, so that the heat treatment composite alloy is obtained; in the normalizing treatment, in the process of raising the temperature to 1015 ℃, the temperature-raising rate is reduced along with the rise of the temperature, and the average temperature-raising rate is 7 ℃/min; in the quenching process, the temperature is increased to 805 ℃, the temperature is kept for 74min, and in the process of cooling to room temperature by water, the cooling speed is reduced along with the reduction of the temperature;
s3, preprocessing: polishing the heat-treated composite alloy obtained in the step S2 for 30min by using sand paper, cleaning by using acetone and then cleaning by using ethanol to obtain a composite alloy; putting 33 parts of titanium powder and 23 parts of graphite powder into a ball mill, uniformly mixing to obtain cladding powder, mixing the cladding powder and a sodium carboxymethyl cellulose solution to form paste, uniformly coating the paste on the surface of the obtained composite alloy, keeping the thickness of the composite alloy to be 2mm, putting the composite alloy into an electric furnace, setting the temperature of the electric furnace to be 164 ℃, preserving the heat for 2.9 hours, and cooling the composite alloy to room temperature along with the furnace to obtain a pretreated ball; the titanium powder comprises the following components in percentage by mass: 0.13% of C, As: 0.55%, Ti: 1.3%, Fe: 0.25%, Pb: 0.029%, N: 0.046%, O: 0.1%, H: 0.01 percent, and the balance of Ti;
s4, reacting nitrogen arc cladding: putting the pretreated ball obtained in the step S3 into a reaction nitrogen arc cladding system for reaction nitrogen arc cladding to obtain a cladding ball, wherein the reaction nitrogen arc cladding system adopts an argon arc welding machine, tungsten with a high melting point is used as a cathode, the pretreated ball is used as an anode, and nitrogen is used as a protective gas and a reaction gas; the parameters of the reaction nitrogen arc cladding process are as follows: cladding current 175A, nitrogen flow 14L/min.
In one embodiment, the pouring and mold opening after the molten steel is completely solidified comprises the following steps: manufacturing a casting blank forming die, a molten steel collector and a molten steel flow opening valve body, wherein the casting blank forming die is a universal blank forming die, the molten steel collector is structurally a graphite crucible and is provided with a bottom opening, the bottom opening is internally provided with a molten steel flow opening valve body, and the molten steel flow opening valve body is adaptive to block the bottom opening in an initial state; one end of the molten steel flow channel is communicated with the valve body of the molten steel flow outlet at the bottom of the molten steel collector; the method comprises the following steps of (1) containing molten steel in a medium-frequency induction smelting furnace into a molten steel collector, opening a valve body of a molten steel flow port to enable molten steel with slag at the bottom of the molten steel collector to flow into a molten steel flow channel, arranging a machine vision detector at an outlet of the molten steel flow channel, and shutting off the valve body of the molten steel flow port when the content of the slag in the molten steel is detected to be reduced to a set steel slag content limiting detection standard; the edge of the molten steel collector is connected with a plurality of collector supports, the collector supports are provided with a mold approach sensor, and when the mold approach sensor senses that a casting blank forming mold approaches, the controller controls the suspension state of the molten steel collector to enable one side of the molten steel collector, which is sensed by the mold approach sensor to approach the casting blank forming mold, to incline downwards; enabling the deslagging molten steel at the upper part of the molten steel collector to flow out to a casting blank forming die through one side of the molten steel collector; the lower molten steel with slag flows into a molten steel collector with slag through the molten steel flow channel; a pressure sensor is arranged at the bottom of the casting blank forming die, and after the pressure sensor detects that the molten steel injected into the casting blank forming die reaches the specified weight, the new casting blank forming die is replaced to continue to inject the molten steel; and opening the mold after the molten steel is completely solidified.
In the blank forming process, the impurity content of the blank is lower through liquid-slag level separation.
In one embodiment, in S2, in the normalizing process, the decreasing the temperature-increasing rate with an increase in temperature in the process of increasing the temperature to 980-: the blank space placement and the heating of the space where the blank to be heated is located are carried out through an electric heating wire heating support plate, a heat insulation radiation-proof plate, a blank heat-insulation cover and a temperature-resistant fan, and the heated blank is uniformly heated, wherein two ends of the electric heating wire heating support plate are respectively connected with a heating negative electrode and a heating positive electrode; the heating wire heating supporting plate is provided with a plurality of heat insulation supporting points, a heat insulation radiation protection plate is horizontally arranged on the heat insulation supporting points, the contact surface of the heat insulation radiation protection plate and the heat insulation supporting points is flat, the other side of the heat insulation radiation protection plate is provided with a plurality of blank bottom space supporting points, the number of the heat insulation supporting points and the number of the blank bottom space supporting points are not less than 3, the heat insulation supporting points and the blank bottom space supporting points are used for isolating single-side heating heat conduction and heat radiation of the blank bottom, and supporting and stable placement of the blank for comprehensive and uniform heating in a located space are provided; the blank heat-insulating cover is fixedly covered on the upper end of the heating wire heating supporting plate; the bottom end of the heating wire heating supporting plate and the blank heat-insulating cover body are provided with a plurality of temperature detection probes for detecting the heating temperature of the blank;
the blank heat-insulating cover is divided into an upper part and a lower part, the lower part is provided with an opening to cover the heating wire heating supporting plate, and the upper part is provided with a temperature-resistant fan which is used for uniformly distributing heat in an airflow accelerating flowing space in the blank heat-insulating cover; the heating negative electrode and the heating positive electrode are respectively connected with the positive electrode and the negative electrode of the power supply; when the heating negative electrode and the heating positive electrode are electrified, the heating wire heating supporting plate is electrically heated, the heat insulation radiation-proof plate arranged on the heat insulation fulcrum of the heating wire heating supporting plate isolates the direct heating and the non-uniform heat radiation of the bottom, and meanwhile, the heat-resistant fan rotates to accelerate the airflow in the blank heat-insulation cover to flow so as to uniformly heat the blank;
when the blank is heated, the temperature detection probe detects the temperature of a heating space in the blank heat-insulating cover in real time, the actual temperature of the blank is calculated according to the temperature of the heating space and the heat conduction characteristic of the blank, the temperature detection probe feeds a detected temperature signal back to the control operation system, the control operation system performs control calculation according to a set temperature-rising program, and then the currents of a heating negative electrode and a heating positive electrode on two sides of a heating-up supporting plate of an electric heating wire are adjusted, the rotating speed of a temperature-resistant fan is adjusted, and the temperature-rising rate is reduced along with the rise of the temperature.
Through even space heating and the real-time control of rising temperature, make the heating process material be heated more evenly, temperature control is more accurate, further improves material performance.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all equivalent structural changes made by using the contents of the present specification, or any other related technical fields directly or indirectly, are included in the scope of the present invention.
Claims (10)
1. A corrosion-resistant high-ductility composite alloy for manufacturing new energy batteries is characterized in that: the composition comprises the following components in percentage by mass: 0.02-0.06% of C, 0.38-0.86% of Mn, 0.01-0.03% of B, Ti: 0.53-0.81%, Ni: 0.21-0.45%, Cr: 5-9.8%, As: 0.11-0.15%, V: 0.7-1.0%, Re 0.2-0.5%, Mg: 0.01-0.038%, Zr: 0.01-0.015%, Cu: 0.01-0.03%, Rh: 0.01 to 0.035 percent, less than or equal to 0.028 percent of PT, less than or equal to 0.033 percent of PD and the balance of Fe and inevitable impurities;
the method for preparing the composite alloy comprises the following steps:
s1, smelting: adding scrap steel into a medium-frequency induction smelting furnace, heating to 1500-;
s2, heat treatment: normalizing, quenching and high-temperature tempering the obtained blank in sequence; in the normalizing treatment, the temperature is raised to 980-1030 ℃, the temperature is kept for 50-80min, and the air is cooled to the room temperature; in the quenching treatment, the temperature is raised to 800-820 ℃, the temperature is kept for 30-75min, and the water is cooled to the room temperature; in the high-temperature tempering treatment, the temperature is increased to 530 ℃ for 500-;
s3, preprocessing: polishing the heat-treated composite alloy obtained in the step S2 by using sand paper, and cleaning by using acetone and ethanol to obtain a composite alloy; putting 15-35 parts of titanium powder and 20-35 parts of graphite powder into a ball mill, uniformly mixing to obtain cladding powder, mixing the cladding powder and an adhesive into paste, uniformly coating the paste on the surface of the obtained composite alloy, wherein the thickness of the paste is 1-3mm, then putting the paste into an electric furnace, setting the temperature of the electric furnace at 160-180 ℃, preserving heat for 2-3.5h, and cooling the paste to room temperature along with the furnace to obtain a pretreatment ball; the titanium powder comprises the following components in percentage by mass: 0.1-0.15% of C, As: 0.2-0.8%, Ti: 0.6-1.8%, Fe: 0.2-0.3%, Pb: 0.02-0.06%, N: 0.02 to 0.08%, O: 0.1-0.55%, H: 0.01-0.03 percent of Ti, and the balance of Ti;
s4, reacting nitrogen arc cladding: putting the pretreated ball obtained in the step S3 into a reaction nitrogen arc cladding system for reaction nitrogen arc cladding to obtain a composite alloy, wherein the reaction nitrogen arc cladding system adopts an argon arc welding machine, tungsten with a high melting point is used as a cathode, the pretreated ball is used as an anode, and nitrogen is used as a protective gas and a reaction gas; the parameters of the reaction nitrogen arc cladding process are as follows: cladding current 150-.
2. The corrosion-resistant high-ductility composite alloy for manufacturing new energy batteries according to claim 1, wherein: the composition comprises the following components in percentage by mass: 0.045% of C, 0.73% of Mn, 0.02% of B, Ti: 0.53%, Ni: 0.35%, Cr: 8.6%, As: 0.14%, V: 0.75%, Re: 0.33%, Mg: 0.025%, Zr: 0.014%, Cu: 0.025%, Rh: 0.026%, PT: 0.019%, PD: 0.03%, and the balance of Fe and inevitable impurities.
3. The corrosion-resistant high-ductility composite alloy for manufacturing new energy batteries according to claim 1, wherein: in S3, the binder is sodium carboxymethyl cellulose solution or water glass.
4. The corrosion-resistant high-ductility composite alloy for manufacturing new energy batteries according to claim 1, wherein: in S1, adding scrap steel into a medium-frequency induction smelting furnace, heating to 1513 ℃, keeping the temperature for 25min, adding ferrovanadium, adding ferrosilicon and ferromanganese after complete melting, heating to 1545 ℃ until complete melting, adding nickel alloy, silicon-calcium alloy and ferrozirconium, completely melting all raw materials to obtain molten steel, pouring, opening the mold after the molten steel is completely solidified, and cooling the furnace to room temperature to obtain a blank; the pouring and die sinking after the molten steel is completely solidified comprises the following steps: manufacturing a casting blank forming die, a molten steel collector and a molten steel flow opening valve body, wherein the casting blank forming die is a universal blank forming die, the molten steel collector is structurally a graphite crucible and is provided with a bottom opening, the bottom opening is internally provided with a molten steel flow opening valve body, and the molten steel flow opening valve body in an initial state is adaptive to block the bottom opening; one end of the molten steel flow channel is communicated with the valve body of the molten steel flow outlet at the bottom of the molten steel collector; molten steel in the medium-frequency induction smelting furnace is filled into the molten steel collector, the valve body of the molten steel circulation port is opened, molten steel with slag at the bottom of the molten steel collector flows into the molten steel flow channel, a machine vision detector is arranged at the outlet of the molten steel flow channel, and the valve body of the molten steel circulation port is closed when the content of the slag in the molten steel is detected to be reduced to a set steel slag content limit detection standard; the edge of the molten steel collector is connected with a plurality of collector supports, the collector supports are provided with a mold approach sensor, and when the mold approach sensor senses that a casting blank forming mold approaches, the controller controls the molten steel collector to be in a suspension state, so that one side of the molten steel collector, which is sensed by the mold approach sensor to approach the casting blank forming mold, inclines downwards; enabling slag-removed molten steel at the upper part of the molten steel collector to flow out of a casting blank forming die through one side of the molten steel collector; the lower molten steel with slag flows into a molten steel collector with slag through the molten steel flow channel; a pressure sensor is arranged at the bottom of the casting blank forming die, and after the pressure sensor detects that the molten steel injected into the casting blank forming die reaches the specified weight, the new casting blank forming die is replaced to continue to inject the molten steel; and opening the mold after the molten steel is completely solidified.
5. The corrosion-resistant high-ductility composite alloy for manufacturing new energy batteries according to claim 1, wherein: in S2, in the normalizing treatment, the temperature is increased to 1015 ℃, the temperature is kept for 55min, and the air is cooled to the room temperature; in the quenching treatment, the temperature is raised to 805 ℃, the temperature is kept for 74min, and the water is cooled to the room temperature; in the high-temperature tempering treatment, the temperature is raised to 505 ℃, the temperature is kept for 145min, and the water is cooled to the room temperature, so that the heat-treated composite alloy is obtained.
6. The corrosion-resistant high-ductility composite alloy for manufacturing new energy batteries according to claim 1, wherein: in S2, in the normalizing process, the temperature rise rate decreases with the temperature rise in the course of raising the temperature to 980-1030 ℃; the decreasing rate of temperature rise with increasing temperature comprises: the blank space placement and the heating of the space where the blank to be heated is located are carried out through an electric heating wire heating support plate, a heat insulation radiation-proof plate, a blank heat-insulation cover and a temperature-resistant fan, and the heated blank is uniformly heated, wherein two ends of the electric heating wire heating support plate are respectively connected with a heating negative electrode and a heating positive electrode; the heating wire heating supporting plate is provided with a plurality of heat insulation supporting points, a heat insulation radiation-proof plate is horizontally placed on the heat insulation supporting points, the contact surface of the heat insulation radiation-proof plate and the heat insulation supporting points is flat, the other side of the heat insulation radiation-proof plate is provided with a plurality of blank bottom space supporting points, the number of the heat insulation supporting points and the number of the blank bottom space supporting points are not less than 3, the heat insulation supporting points and the blank bottom space supporting points are used for isolating single-side heating heat conduction and heat radiation of the bottom of a blank, and supporting and stable placement for comprehensively and uniformly heating and heating the blank in a located space are provided; the blank heat-insulating cover is fixedly covered on the upper end of the heating wire heating supporting plate; the bottom end of the heating wire heating supporting plate and the blank heat-insulating cover body are provided with a plurality of temperature detection probes for detecting the heating temperature of the blank;
the blank heat-insulating cover is divided into an upper part and a lower part, the lower part is provided with an opening to cover the heating wire heating supporting plate, and the upper part is provided with a temperature-resistant fan which is used for uniformly distributing heat in an airflow accelerating flowing space in the blank heat-insulating cover; the heating negative electrode and the heating positive electrode are respectively connected with the positive electrode and the negative electrode of the power supply; when the heating negative electrode and the heating positive electrode are electrified, the heating wire heating supporting plate is electrically heated, the heat insulation radiation protection plate arranged on the heat insulation fulcrum of the heating wire heating supporting plate isolates direct heating and non-uniform heat radiation at the bottom, and meanwhile, the temperature-resistant fan rotates to accelerate the airflow in the blank heat insulation cover to uniformly heat the blank;
when the blank is heated, the temperature detection probe detects the temperature of a heating space in the blank heat-insulating cover in real time, the actual temperature of the blank is calculated according to the temperature of the heating space and the heat conduction characteristic of the blank, the temperature detection probe feeds a detected temperature signal back to the control operation system, the control operation system performs control calculation according to a set temperature-rising program, and then the currents of a heating negative electrode and a heating positive electrode on two sides of a heating-up supporting plate of an electric heating wire are adjusted, the rotating speed of a temperature-resistant fan is adjusted, and the temperature-rising rate is reduced along with the rise of the temperature.
7. The corrosion-resistant high-ductility composite alloy for manufacturing new energy batteries according to claim 1, wherein: in S2, in the quenching treatment, the temperature is raised to 800-820 ℃, the temperature is kept for 30-75min, and the cooling speed is reduced along with the reduction of the temperature in the process of water cooling to the room temperature.
8. The corrosion-resistant high-ductility composite alloy for manufacturing the new energy battery as claimed in claim 1, wherein: in S3, the titanium powder comprises the following components in percentage by mass: 0.13% of C, As: 0.55%, Ti: 1.3%, Fe: 0.25%, Pb: 0.029%, N: 0.046%, O: 0.1%, H: 0.01 percent, and the balance of Ti.
9. The corrosion-resistant high-ductility composite alloy for manufacturing new energy batteries according to claim 1, wherein: in S3, 20 parts of titanium powder and 30 parts of graphite powder are put into a ball mill to be uniformly mixed to obtain cladding powder, the cladding powder and an adhesive are mixed into paste to be uniformly coated on the surface of the obtained composite alloy, the thickness of the cladding powder is 2mm, the cladding powder and the adhesive are put into an electric furnace, the temperature of the electric furnace is set to be 170 ℃, the heat is preserved for 3 hours, and the pretreatment ball is obtained after the cladding powder and the adhesive are cooled to room temperature along with the furnace.
10. The corrosion-resistant high-ductility composite alloy for manufacturing new energy batteries according to claim 1, wherein: in S4, the parameters of the reaction nitrogen arc cladding process are specifically as follows: cladding current 175A, nitrogen flow 14L/min.
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