CN114086086B - Nano-phase carbon-nitrogen composite particle reinforced invar alloy wire and preparation method thereof - Google Patents

Nano-phase carbon-nitrogen composite particle reinforced invar alloy wire and preparation method thereof Download PDF

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CN114086086B
CN114086086B CN202111307778.3A CN202111307778A CN114086086B CN 114086086 B CN114086086 B CN 114086086B CN 202111307778 A CN202111307778 A CN 202111307778A CN 114086086 B CN114086086 B CN 114086086B
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wire rod
heat treatment
aging heat
nitrogen
invar alloy
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CN114086086A (en
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孙中华
吴迎飞
翟永臻
王育飞
陈文�
张坤
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HBIS Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/74—Methods of treatment in inert gas, controlled atmosphere, vacuum or pulverulent material
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/06—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of rods or wires
    • C21D8/065—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of rods or wires of ferrous alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • C22B9/16—Remelting metals
    • C22B9/18—Electroslag remelting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/04—Making ferrous alloys by melting
    • C22C33/06—Making ferrous alloys by melting using master alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/46—Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium

Abstract

A nanophase carbon-nitrogen composite particle enhanced invar alloy wire and a preparation method thereof are disclosed, wherein the wire comprises the following chemical components by mass: 0.29 to 0.33 percent of C, 37.5 to 39.8 percent of Ni; 0.8 to 1.5% of Mo, 0.75 to 1.15% of Cr, 0.9 to 1.3% of V, 0.01 to 0.025% of N, 0.3 to 0.7% of Mn, and the balance of Fe and inevitable impurities; the preparation method comprises the working procedures of vacuum melting, electroslag remelting, square billet forging, rolling, solution treatment, cold drawing and aging heat treatment; the aging heat treatment process is carried out in a hydrogen annealing furnace, the temperature of the aging heat treatment is 550-700 ℃, and the time is 5-30 min. The invention adopts two-stage processing of cold drawing-aging heat treatment, the grain size of the precipitated phase carbonitride of the invar alloy wire is 10-120 nm, the mechanical property is good, and the production period is greatly shortened.

Description

Nano-phase carbon-nitrogen composite particle reinforced invar alloy wire and preparation method thereof
Technical Field
The invention belongs to the technical field of metallurgy, and particularly relates to a nanophase carbon-nitrogen composite particle enhanced invar alloy wire and a preparation method thereof.
Background
Invar (also known as invar) has a very low linear expansion coefficient, and is widely used as a material for parts such as high-definition kinescopes, precision balance rockers, microwave communication waveguides and laser collimator cavities. However, the invar alloy has a single-phase austenite structure at room temperature and cannot be strengthened by transformation, resulting in low yield strength and tensile strength. In recent years, new products such as invar core materials for double-capacity wires, invar sheets for Liquefied Natural Gas (LNG) ships, invar molds for aviation composite materials and the like have higher requirements on the strength performance of the materials, the strengthening technology of invar alloys is improved, the strengthening mechanism of the invar alloys is explored, and the invar core materials are more and more highly regarded by main industrialized countries. At present, the conventional strengthening modes of invar, such as solid solution strengthening, work hardening and the like, are difficult to meet the performance requirements of high strength and high elongation of invar wire materials.
In early studies, researchers simply added W, V alloy elements (patent No. ZL 200510029930.0) to invar, and hoped that the strength of invar steel would be improved by forming carbide precipitation phase, but this method easily forms coarse carbide particles, which affects the toughness and torsion performance of invar steel.
Terrestrial building (patent number ZL 201110201300.2) proposes introducing an intermetallic compound Ni into a traditional invar alloy3(Ti, Al) is used as a strengthening phase, but TiN particles formed in the smelting process of Ti have high melting point and high redissolution temperature, are difficult to eliminate in subsequent cold and hot processing, and can seriously affect the mechanical and physical properties of the wire. In order to suppress the increase in the thermal expansion coefficient, elements such as Co and W must be added, which also increases the production cost of the invar steel.
Researchers (application No. 201911275204.5) have proposed a method of improving the strength of invar steel by adding elements such as Nb and Co based on the components of the traditional invar alloy and combining the processes of solution treatment, drawing, intermediate annealing, secondary drawing and the like. However, the method uses expensive Nb and Co elements, thereby increasing the manufacturing cost of the invar steel; meanwhile, the addition of Nb can increase the probability of segregation after the smelting of invar steel, and has certain influence on the performance of products.
Meanwhile, in the wire processing technologies disclosed in the above three patents, the processes of cold drawing, intermediate heat treatment and secondary cold drawing are all used. After the secondary cold drawing, the plasticity, toughness and torsion performance of the wire can be reduced due to the action of work hardening; the saponification layer formed after drawing also increases the subsequent processing difficulty; meanwhile, cold drawing, intermediate heat treatment and secondary cold drawing can also reduce the production continuity and prolong the production period.
Disclosure of Invention
In order to solve the technical problems, the invention provides a nano-phase carbon-nitrogen composite particle reinforced invar alloy wire and a preparation method thereof. The technical scheme adopted by the invention is as follows:
a nanophase carbon-nitrogen composite particle enhanced invar alloy wire comprises the following chemical components in percentage by mass: 0.29 to 0.33 percent of C, 37.5 to 39.8 percent of Ni; 0.8 to 1.5% of Mo, 0.75 to 1.15% of Cr, 0.9 to 1.3% of V, 0.01 to 0.025% of N, 0.3 to 0.7% of Mn, and the balance of Fe and inevitable impurities; after the invar alloy wire is subjected to aging heat treatment, the size of precipitated phase carbonitride particles is 10-120 nm.
The invar alloy wire rod has the diameter of 4.5-5.5 mm, the tensile strength of more than or equal to 1250MPa, the elongation after fracture of more than or equal to 5 percent, and the thermal expansion coefficient of less than or equal to 2.9 multiplied by 10-6The number of turns is more than or equal to 120 turns at/DEG C.
The preparation method of the nano-phase carbon-nitrogen composite particle enhanced invar alloy wire rod comprises the working procedures of vacuum melting, electroslag remelting, square billet forging, rolling, solution treatment, cold drawing and aging heat treatment.
In the vacuum melting process, after the alloy raw materials are completely melted down, manganese nitride accounting for 0.35-0.85% of the total weight of the melted alloy raw materials is added, and nitrogen is filled at the same time, wherein the pressure of the nitrogen is kept at 30000-80000 Pa.
The electroslag remelting process is started by solid slag, the slag system is pre-melted slag, and the composition of the slag system is CaF240 to 55 parts of Al2O320 to 25 parts, 25 to 15 parts of CaO and 15 to 5 parts of MgO; the melting speed is controlled to be 4 plus or minus 0.2kg/min, nitrogen protection is adopted in the whole process, and the oxygen content in the protective smoke hood is controlled to be less than or equal to 100 ppm.
The rolling procedure is to roll the forged square billet into a wire rod with the diameter of 12-16 mm; the initial rolling temperature is 1170-1200 ℃, and the final rolling temperature is 880-930 ℃; and immediately cooling the rolled wire rod to room temperature by water.
And in the solid solution treatment process, the wire rod is placed into a heating furnace filled with nitrogen, the temperature is raised to 1180-1230 ℃ of solid solution temperature, the wire rod is taken out after heat preservation for 1.5-3.5 hours, and water cooling is carried out.
In the cold drawing process, sand blasting is firstly carried out to remove oxide skin, and then cold drawing is carried out to obtain a wire rod with the diameter of 4.5-5.5 mm; the single-pass surface reduction amount is 25-35%, and the total surface reduction amount is 80-92%.
The aging heat treatment process is carried out in a hydrogen annealing furnace, the temperature of the aging heat treatment is 550-700 ℃, and the time of the aging heat treatment is 5-30 min.
By using the component system and the process, the carbonitride particles with nano-scale can be obtained, so that the parameters of the prepared invar alloy wire material, such as strength, plasticity, torsion property, thermal expansion coefficient and the like, are remarkably improved, Co element used in the conventional process is completely replaced, and the cost of alloy raw materials is reduced; in addition, the process reduces the traditional three-stage processing process of cold drawing, intermediate heat treatment and secondary cold drawing into a two-stage processing process of cold drawing and aging heat treatment, greatly shortens the production period, improves the process efficiency and reduces the manufacturing cost.
According to the method, initial carbonitrides generated in the hot rolling wire rod process are dissolved back through solution treatment to achieve a single austenite structure, the dislocation density of a matrix structure is improved in a cold drawing process, more driving force and nucleation positions are provided for precipitation of nano-scale particles, and then the carbonitride particles are rapidly precipitated on a severely deformed austenite matrix through low-temperature short-time aging heat treatment and do not have enough growth driving energy, so that the precipitated particles with the size of 10-120 nm are obtained.
The nano-phase carbon-nitrogen composite particle reinforced invar alloy wire rod has the diameter of 4.5-5.5 mm, the tensile strength of more than or equal to 1250MPa, the elongation after breakage of more than or equal to 5 percent (250mm gauge length), and the thermal expansion coefficient of less than or equal to 2.9 multiplied by 10-6The number of turns is more than or equal to 120 turns at room temperature of 230 ℃, and the performance requirements of high strength and high elongation are met.
Drawings
FIG. 1 is an SEM topography of precipitated phase particles in the wire rod after the aging heat treatment in example 1;
FIG. 2 is a transmission electron micrograph of the wire rod after the aging heat treatment in example 1;
FIG. 3 is an SEM topography of precipitated phase particles in the wire rod after the aging heat treatment in example 2;
FIG. 4 is a transmission electron micrograph of the wire rod after the aging heat treatment in example 2;
FIG. 5 is an SEM topography of precipitated phase particles in the wire rod after the aging heat treatment in example 3;
FIG. 6 is a transmission electron micrograph of the wire rod after the aging heat treatment of example 3;
FIG. 7 is a graph showing the distribution of C, N, Mo and V elements in the Electron Probe (EPMA) surface scanning state (region in the box) of the precipitated particles of the wire rod after the aging heat treatment in example 1.
Detailed Description
Example 1
The chemical composition and the mass percentage content of the nano-phase carbon-nitrogen composite particle reinforced invar alloy wire rod of the embodiment are shown in table 1. The production method comprises the working procedures of vacuum melting, electroslag remelting, square billet forging, rolling, solution treatment, cold drawing and aging heat treatment, and the specific process steps are as follows:
in the vacuum melting process, after the alloy raw materials are completely melted down, manganese nitride alloy accounting for 0.57 percent of the weight of the alloy raw materials is added, and nitrogen gas of 60kPa is filled simultaneously, and the time of complete melting down is 2 hours. Then carrying out electroslag remelting, starting by adopting solid slag, wherein the slag system is premelted slag and comprises CaF240 parts of Al2O325 parts of CaO, 25 parts of CaO and 10 parts of MgO; the whole process adopts nitrogen protection, and the oxygen content in the protection hood is controlled to be 20-75 ppm; the melting speed is 4 plus or minus 0.2 kg/min. Rolling the forged square billet into a wire rod with the diameter of 13.5mm through a forging process; the initial rolling temperature is 1180 ℃, and the final rolling temperature is 880 ℃; and immediately cooling the rolled wire rod to room temperature by water. And then putting the wire rod into a heating furnace filled with nitrogen for solution treatment, heating to 1195 ℃, keeping the temperature for 1.5h, taking out, and cooling by water. The steel wire rod after the solution treatment is subjected to sand blasting to remove oxide skin, and then is subjected to cold drawing to form a wire rod with the diameter of 4.5mm, wherein the single-pass surface reduction amount is 25-35%, and the total surface reduction amount is 88.9%. And finally, carrying out aging heat treatment in a hydrogen annealing furnace, wherein the aging heat treatment temperature is 600 ℃, and the time is 10 min.
The mechanical properties of the nanophase carbon nitrogen composite particle reinforced invar alloy wire rod obtained in the embodiment are shown in table 2. The SEM topography of precipitated phase particles in the wire rod after aging heat treatment is shown in figure 1, the transmission electron microscope microstructure is shown in figure 2, a large number of precipitated phase particles with small sizes are dispersed in a matrix structure as shown in figure 1, and the precipitated phase is elliptic or nearly spherical in appearance and is 10-15 nm in size range as shown in figure 2. Fig. 7 shows the Electron Probe (EPMA) surface scanning state (region in the box) of the precipitated particles of the wire rod after the aging heat treatment, and as can be seen from fig. 7, the precipitated particles include C, N, Mo, and V elements and are identified as carbonitride-composite particles containing both V and Mo alloy elements.
Example 2
The chemical composition and the mass percentage content of the nanophase carbon-nitrogen composite particle reinforced invar alloy wire rod of the embodiment are shown in table 1. The production method comprises the working procedures of vacuum melting, electroslag remelting, square billet forging, rolling, solution treatment, cold drawing and aging heat treatment, and the specific process steps are as follows:
in the vacuum melting process, after the alloy raw materials are completely melted down, manganese nitride alloy accounting for 0.68 percent of the weight of the alloy raw materials is added, and 70kPa nitrogen is charged simultaneously, wherein the time of complete melting down is 2.2 hours. Then carrying out electroslag remelting, starting by adopting solid slag, wherein the slag system is premelted slag and comprises CaF245 parts of Al2O320 portions of CaO, 20 portions of CaO and 15 portions of MgO; the whole process adopts nitrogen protection, and the oxygen content in the protection smoke hood is controlled to be 40-96 ppm; the melting speed is 4 plus or minus 0.2 kg/min. Rolling the forged square billet into a wire rod with the diameter of 14mm through a forging process; the initial rolling temperature is 1190 ℃, and the final rolling temperature is 900 ℃; and immediately cooling the wire rod to room temperature after rolling. And then putting the wire rod into a heating furnace filled with nitrogen for solution treatment, heating to 1200 ℃, keeping the temperature for 2 hours, taking out, and cooling by water. And (3) carrying out sand blasting treatment on the wire rod subjected to the solution treatment to remove oxide skin, and then carrying out cold drawing to obtain a wire rod with the diameter of 5.5mm, wherein the single-pass surface reduction amount is 25-32%, and the total surface reduction amount is 84.6%. And finally, carrying out aging heat treatment in a hydrogen annealing furnace at the temperature of 620 ℃ for 8 min. The mechanical properties of the nanophase carbon nitrogen composite particle reinforced invar alloy wire obtained in this example are shown in table 2. The SEM topography of precipitated phase particles in the wire rod after aging heat treatment is shown in figure 3, the transmission electron microscope microstructure is shown in figure 4, from figure 3, a relatively small number of precipitated phase particles are dispersed in a matrix structure, and from figure 4, the precipitated phase is in an ellipse or a near circleSpherical appearance, size range 20-45 nm.
Example 3
The chemical composition and the mass percentage content of the nanophase carbon-nitrogen composite particle reinforced invar alloy wire rod of the embodiment are shown in table 1. The production method comprises the working procedures of vacuum melting, electroslag remelting, square billet forging, rolling, solution treatment, cold drawing and aging heat treatment, and the specific process steps are as follows:
in the vacuum melting process, after the alloy raw materials are completely melted down, manganese nitride alloy accounting for 0.82 percent of the weight of the alloy raw materials is added, and nitrogen gas of 75kPa is filled simultaneously, and the time of complete melting down is 2 hours. Then carrying out electroslag remelting, starting by adopting solid slag, wherein the slag system is premelted slag and comprises CaF245 parts of Al2O320 portions of CaO, 25 portions of CaO and 10 portions of MgO; adopting nitrogen protection in the whole process, and controlling the oxygen content in the protection smoke hood to be 35-90 ppm; the melting speed is 4 plus or minus 0.2 kg/min. Rolling the forged square billet into a wire rod with the diameter of 14.5mm through a forging process; the initial rolling temperature is 1190 ℃, and the final rolling temperature is 890 ℃; and immediately cooling the wire rod to room temperature after rolling. And then putting the wire rod into a heating furnace filled with nitrogen for solution treatment, heating to 1210 ℃, keeping the temperature for 2.5 hours, then taking out, and cooling by water. And (3) carrying out sand blasting on the wire rod subjected to the solution treatment to remove oxide skin, and then carrying out cold drawing to obtain a wire rod with the diameter of 5.5mm, wherein the single-pass surface reduction amount is 27-32%, and the total surface reduction amount is 85.6%. And finally, carrying out aging heat treatment in a hydrogen annealing furnace, wherein the aging heat treatment temperature is 650 ℃ and the time is 7 min.
The mechanical properties of the nanophase carbon nitrogen composite particle reinforced invar alloy wire rod obtained in the embodiment are shown in table 2. The SEM topography of precipitated phase particles in the wire rod after aging heat treatment is shown in figure 5, the transmission electron microscope microstructure is shown in figure 6, a certain amount of precipitated phase particles are dispersed in a matrix structure as shown in figure 5, the precipitated phase is elliptic or nearly spherical as shown in figure 6, and the size range is 30-85 nm.
Example 4
The chemical composition and the mass percentage content of the nanophase carbon-nitrogen composite particle reinforced invar alloy wire rod of the embodiment are shown in table 1. The production method comprises the working procedures of vacuum melting, electroslag remelting, square billet forging, rolling, solution treatment, cold drawing and aging heat treatment, and the specific process steps are as follows:
in the vacuum melting process, after the alloy raw materials are completely melted down, manganese nitride alloy accounting for 0.35 percent of the weight of the alloy raw materials is added, and meanwhile, 44kPa nitrogen is filled, and the time of complete melting down is 3 hours. Then carrying out electroslag remelting, starting by adopting solid slag, wherein the slag system is premelted slag and comprises CaF255 parts by weight of Al2O322 parts of CaO, 18 parts of CaO and 5 parts of MgO; the whole process adopts nitrogen protection, and the oxygen content in the protection hood is controlled to be less than or equal to 50 ppm; the melting speed is 4 plus or minus 0.2 kg/min. Rolling the forged square billet into a wire rod with the diameter of 12mm through a forging process; the initial rolling temperature is 1177 ℃, and the final rolling temperature is 925 ℃; and immediately cooling the wire rod to room temperature after rolling. And then putting the wire rod into a heating furnace filled with nitrogen for solution treatment, heating to 1188 ℃, keeping the temperature for 3.5 hours, then taking out, and cooling by water. And (3) carrying out sand blasting on the wire rod subjected to the solution treatment to remove oxide skin, and then carrying out cold drawing to obtain a wire rod with the diameter of 5.3mm, wherein the single-pass surface reduction amount is 25-30%, and the total surface reduction amount is 80.5%. And finally, carrying out aging heat treatment in a hydrogen annealing furnace at the temperature of 579 ℃ for 22 min.
The mechanical properties of the nanophase carbon nitrogen composite particle reinforced invar alloy wire obtained in this example are shown in table 2. After aging heat treatment, precipitated phase particles in the wire are dispersed in a matrix structure, the precipitated phase is in an oval or nearly spherical appearance, and the size range is 40-110 nm.
Example 5
The chemical composition and the mass percentage content of the nano-phase carbon-nitrogen composite particle reinforced invar alloy wire rod of the embodiment are shown in table 1. The production method comprises the working procedures of vacuum melting, electroslag remelting, square billet forging, rolling, solution treatment, cold drawing and aging heat treatment, and the specific process steps are as follows:
in the vacuum melting process, after the alloy raw materials are completely melted down, manganese nitride alloy accounting for 0.75 percent of the weight of the alloy raw materials is added, and 80kPa nitrogen is filled simultaneously, and the time of complete melting down is 1.5 hours. Then carrying out electroslag remelting, starting by adopting solid slag, wherein the slag system is premelted slag and comprises CaF253 parts of Al2O324 parts of CaO, 15 parts of CaO and 8 parts of MgO; the whole process adopts nitrogen protection, and the oxygen content in the protection hood is controlled to be less than or equal to 80 ppm; the melting speed is 4 plus or minus 0.2 kg/min. Rolling the forged square billet into a wire rod with the diameter of 15.5mm through a forging process; the initial rolling temperature is 1200 ℃, and the final rolling temperature is 887 ℃; and immediately cooling the wire rod to room temperature after rolling. And then putting the wire rod into a heating furnace filled with nitrogen for solution treatment, heating the wire rod at 1225 ℃, keeping the temperature for 2 hours, taking out the wire rod, and cooling the wire rod by water. The steel wire rod after the solution treatment is subjected to sand blasting to remove oxide skin, and then is subjected to cold drawing to form a wire rod with the diameter of 5.1mm, wherein the single-pass surface reduction amount is 26-31%, and the total surface reduction amount is 89.2%. And finally, carrying out aging heat treatment in a hydrogen annealing furnace at the temperature of 550 ℃ for 25 min.
The mechanical properties of the nanophase carbon nitrogen composite particle reinforced invar alloy wire rod obtained in the embodiment are shown in table 2. After aging heat treatment, precipitated phase particles in the wire are dispersed in a matrix structure, the precipitated phase is in an oval or nearly spherical appearance, and the size range is 28-76 nm.
Example 6
The chemical composition and the mass percentage content of the nanophase carbon-nitrogen composite particle reinforced invar alloy wire rod of the embodiment are shown in table 1. The production method comprises the working procedures of vacuum melting, electroslag remelting, square billet forging, rolling, solution treatment, cold drawing and aging heat treatment, and the specific process steps are as follows:
in the vacuum melting process, after the alloy raw materials are completely melted down, manganese nitride alloy accounting for 0.85 percent of the weight of the alloy raw materials is added, and simultaneously, 55kPa nitrogen is filled, and the time of complete melting down is 2.5 hours. Then carrying out electroslag remelting, starting by adopting solid slag, wherein the slag system is premelted slag and comprises CaF253 parts of Al2O324 parts of CaO, 15 parts of CaO and 8 parts of MgO; the whole process adopts nitrogen protection, and the oxygen content in the protective smoke hood is controlled to be less than or equal to 93 ppm; the melting speed is 4 plus or minus 0.2 kg/min. Rolling the forged square billet into a wire rod with the diameter of 12.0mm through a forging process; the initial rolling temperature is 1185 ℃, and the final rolling temperature is 904 ℃; and immediately cooling the wire rod to room temperature after rolling. And then putting the wire rod into a heating furnace filled with nitrogen for solution treatment, heating at 1180 ℃, keeping the temperature for 200min, taking out, and cooling by water. Solid solutionAnd (3) carrying out sand blasting on the treated wire rod to remove oxide skin, and then carrying out cold drawing to obtain a wire rod with the diameter of 4.7mm, wherein the single-pass surface reduction amount is 25.5-33.5%, and the total surface reduction amount is-84.7%. And finally, carrying out aging heat treatment in a hydrogen annealing furnace at the temperature of 677 ℃ for 5 min.
The mechanical properties of the nanophase carbon nitrogen composite particle reinforced invar alloy wire obtained in this example are shown in table 2. After aging heat treatment, precipitated phase particles in the wire rod are dispersed in a matrix structure, the precipitated phase is in an oval or nearly spherical appearance, and the size range is 45-105 nm.
Example 7
The chemical composition and the mass percentage content of the nano-phase carbon-nitrogen composite particle reinforced invar alloy wire rod of the embodiment are shown in table 1. The production method comprises the working procedures of vacuum melting, electroslag remelting, square billet forging, rolling, solution treatment, cold drawing and aging heat treatment, and the specific process steps are as follows:
in the vacuum melting process, after the alloy raw materials are completely melted down, manganese nitride alloy accounting for 0.42 percent of the weight of the alloy raw materials is added, and 30kPa nitrogen is filled simultaneously, and the time of complete melting down is 1.5 hours. Then electroslag remelting is carried out, solid slag is adopted for starting, the slag system is pre-melted slag, and the composition of the slag system is CaF250 portions of Al2O321 parts of CaO, 23 parts of CaO and 6 parts of MgO; the whole process adopts nitrogen protection, and the oxygen content in the protection smoke hood is controlled to be less than or equal to 99 ppm; the melting speed is 4 plus or minus 0.2 kg/min. Rolling the forged square billet into a wire rod with the diameter of 15.0mm through a forging process; the initial rolling temperature is 1196 ℃, and the final rolling temperature is 930 ℃; and immediately cooling the rolled wire rod to room temperature by water. And then putting the wire rod into a heating furnace filled with nitrogen for solution treatment, heating at 1213 ℃, keeping the temperature for 3h, taking out, and cooling with water. And (3) carrying out sand blasting treatment on the wire rod subjected to the solution treatment to remove oxide skin, and then carrying out cold drawing to obtain a wire rod with the diameter of 4.5mm, wherein the single-pass surface reduction amount is 25.7-31.6%, and the total surface reduction amount is 91%. And finally, carrying out aging heat treatment in a hydrogen annealing furnace, wherein the aging heat treatment temperature is 700 ℃, and the time is 16 min.
The mechanical properties of the nanophase carbon nitrogen composite particle reinforced invar alloy wire rod obtained in the embodiment are shown in table 2. After aging heat treatment, precipitated phase particles in the wire rod are dispersed in a matrix structure, the precipitated phase is in an oval or nearly spherical appearance, and the size range is 30-95 nm.
Example 8
The chemical composition and the mass percentage content of the nano-phase carbon-nitrogen composite particle reinforced invar alloy wire rod of the embodiment are shown in table 1. The production method comprises the working procedures of vacuum melting, electroslag remelting, square billet forging, rolling, solution treatment, cold drawing and aging heat treatment, and the specific process steps are as follows:
in the vacuum melting process, after the alloy raw materials are completely melted down, manganese nitride alloy accounting for 0.50 percent of the weight of the alloy raw materials is added, and nitrogen gas with the pressure of 37kPa is filled simultaneously, and the time of complete melting down is 3 hours. Then carrying out electroslag remelting, starting by adopting solid slag, wherein the slag system is premelted slag and comprises CaF248 parts by weight of Al2O324 parts of CaO, 19 parts of CaO and 9 parts of MgO; the whole process adopts nitrogen protection, and the oxygen content in the protection smoke hood is controlled to be less than or equal to 85 ppm; the melting speed is 4 plus or minus 0.2 kg/min. Rolling the forged square billet into a wire rod with the diameter of 16.0mm through a forging process; the initial rolling temperature is 1170 ℃, and the final rolling temperature is 913 ℃; and immediately cooling the rolled wire rod to room temperature by water. And then putting the wire rod into a heating furnace filled with nitrogen for solution treatment, heating the wire rod at 1230 ℃, keeping the temperature for 2.5 hours, taking out the wire rod, and cooling the wire rod by water. And (3) carrying out sand blasting on the wire rod subjected to the solution treatment to remove oxide skin, and then carrying out cold drawing to obtain a wire rod with the diameter of 4.6mm, wherein the single-pass surface reduction amount is 25.6-34.5%, and the total surface reduction amount is-91.7%. And finally, carrying out aging heat treatment in a hydrogen annealing furnace at the temperature of 564 ℃ for 30 min.
The mechanical properties of the nanophase carbon nitrogen composite particle reinforced invar alloy wire obtained in this example are shown in table 2. After aging heat treatment, precipitated phase particles in the wire rod are dispersed in a matrix structure, the precipitated phase is in an oval or nearly spherical appearance, and the size range is 23-87 nm.
TABLE 1 chemical composition and content (wt%) of invar alloy wire of each example
Examples C Ni Mo Cr V N Mn
1 0.31 39.2 0.93 0.95 0.97 0.013 0.45
2 0.30 38.6 0.89 1.04 0.92 0.017 0.55
3 0.29 39.8 1.23 0.89 1.13 0.021 0.65
4 0.32 38.0 0.80 1.11 1.30 0.015 0.30
5 0.30 37.5 1.35 0.75 1.04 0.010 0.38
6 0.33 38.1 1.44 0.99 1.28 0.025 0.60
7 0.29 39.5 1.07 1.15 1.20 0.020 0.70
8 0.32 37.7 1.50 0.82 0.90 0.023 0.33
TABLE 2 mechanical properties of invar alloy wire rods of the examples
Figure BDA0003340868330000101

Claims (6)

1. A nanophase carbon-nitrogen composite particle enhanced invar alloy wire is characterized by comprising the following chemical components in percentage by mass: 0.29 to 0.33 percent of C, 37.5 to 39.8 percent of Ni; 0.8 to 1.44% of Mo, 0.75 to 1.15% of Cr, 1.04 to 1.3% of V, 0.01 to 0.025% of N, 0.3 to 0.7% of Mn, and the balance of Fe and inevitable impurities;
after the invar alloy wire is subjected to aging heat treatment, the size of precipitated phase carbonitride particles is 10-120 nm; the diameter of the invar alloy wire is 4.5-5.5 mm, the tensile strength is more than or equal to 1250MPa, the elongation after fracture is more than or equal to 5 percent, and the thermal expansion coefficient is less than or equal to 2.9 multiplied by 10-6The number of turns is more than or equal to 120 turns per DEG C;
the preparation method of the invar alloy wire rod comprises the working procedures of vacuum melting, electroslag remelting, square billet forging, rolling, solution treatment, cold drawing and aging heat treatment; in the solid solution treatment process, the wire rod is placed into a heating furnace filled with nitrogen, the temperature is raised to 1180-1230 ℃ of solid solution temperature, the wire rod is taken out after heat preservation for 1.5-3.5 hours, and water cooling is carried out; in the cold drawing process, the single-pass surface reduction amount is 25-35%, and the total surface reduction amount is 80-92%; the aging heat treatment process is carried out in a hydrogen annealing furnace, the temperature of the aging heat treatment is 550-700 ℃, and the time of the aging heat treatment is 5-30 min.
2. The preparation method of the nano-phase carbon-nitrogen composite particle enhanced invar alloy wire rod based on claim 1, which is characterized by comprising the working procedures of vacuum melting, electroslag remelting, square billet forging, rolling, solution treatment, cold drawing and aging heat treatment;
in the solid solution treatment process, the wire rod is placed into a heating furnace filled with nitrogen, the temperature is raised to 1180-1230 ℃ of solid solution temperature, the wire rod is taken out after heat preservation for 1.5-3.5 hours, and water cooling is carried out;
in the cold drawing process, the single-pass surface reduction amount is 25-35%, and the total surface reduction amount is 80-92%;
the aging heat treatment process is carried out in a hydrogen annealing furnace, the temperature of the aging heat treatment is 550-700 ℃, and the time of the aging heat treatment is 5-30 min.
3. The preparation method of the nano-phase carbon-nitrogen composite particle enhanced invar alloy wire rod as claimed in claim 2, wherein in the vacuum melting process, after the alloy raw materials are completely melted down, manganese nitride which is 0.35-0.85% of the total weight of the melted alloy raw materials is added, and nitrogen is filled at the same time, and the pressure of the nitrogen is kept at 30000-80000 Pa.
4. The method for preparing the nano-phase carbon-nitrogen composite particle enhanced invar alloy wire rod as claimed in claim 3, wherein the electroslag remelting process is started by solid slag, and the slag system is pre-melted slag with CaF as the component240 to 55 parts of Al2O320 to 25 parts of CaO, 25 to 15 parts of CaO and 15 to 5 parts of MgO; the melting speed is controlled to be 4 plus or minus 0.2kg/min, nitrogen protection is adopted in the whole process, and the oxygen content in the protective smoke hood is controlled to be less than or equal to 100 ppm.
5. The method for producing the nanophase carbon nitrogen composite particle-reinforced invar alloy wire rod according to claim 4, wherein the rolling step is a step of rolling the forged billet into a wire rod having a diameter of 12 to 16 mm; the initial rolling temperature is 1170-1200 ℃, and the final rolling temperature is 880-930 ℃; and immediately cooling the wire rod to room temperature after rolling.
6. The method for preparing the nano-phase carbon-nitrogen composite particle enhanced invar alloy wire rod according to any one of claims 2 to 5, wherein the cold drawing process comprises removing oxide scales by sand blasting, and then cold drawing to form a wire rod with a diameter of 4.5 to 5.5 mm.
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