CN108193144B - High-strength spring wire with high elastic modulus and preparation method thereof - Google Patents
High-strength spring wire with high elastic modulus and preparation method thereof Download PDFInfo
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- 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
- C22C38/52—Ferrous alloys, e.g. steel alloys containing chromium with nickel with cobalt
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- 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
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/02—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for springs
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- C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
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- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
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- 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
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- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- 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
- C22C38/54—Ferrous alloys, e.g. steel alloys containing chromium with nickel with boron
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Abstract
A high-strength spring wire with high elastic modulus and a preparation method thereof belong to the technical field of high-strength spring wire processes. The spring part with excellent performance is obtained by carrying out different proportions on relatively simple and easily-obtained raw materials, forging and hot rolling after vacuum smelting and consumable smelting, cold-drawing to the final size through different deformation and heat treatment processes, and carrying out heat treatment after winding into a spring. The spring has the advantages of simple operation, low cost and excellent comprehensive performance, and can be used for other spring parts with strict requirements on environment; the preparation method of the spring wire is simple to operate, energy-saving and environment-friendly, and is suitable for industrial large-scale production.
Description
Technical Field
The invention belongs to the technical field of high-strength spring wire processes, and particularly relates to a high-strength spring wire with high elastic modulus and a preparation method thereof. In particular to a high-strength spring wire with high elasticity modulus and good long-term stability and a preparation method thereof.
Background
The stainless spring has the advantages of corrosion resistance, oxidation resistance and the like. The method is widely applied to industries with strict performance requirements, such as electronic and electric appliances, food industry, chemical industry, textile machinery, automobile manufacturing, aviation and the like. Besides being stainless and corrosion resistant, the resulting springs have many other advantages, such as a much better resistance to relaxation (sag) than springs made of spring steel and alloy steel, and even several times better. Because the stainless spring steel has excellent performance which can not be achieved by common carbon spring steel and alloy spring steel, and the requirements of certain departments on the performances of stainless spring, corrosion resistance and the like are more and more urgent and strict, particularly the development of small springs (the diameter of common spring steel wires is difficult to thin), the application range of the stainless spring steel is continuously expanded, and the using amount is continuously increased. Stainless spring wires widely used at home and abroad are roughly classified into three types: phase-change martensitic steel wire, deformation-strengthened austenitic steel wire and precipitation-hardened semi-austenitic steel wire.
For semi-austenitic precipitation hardening stainless steels with a higher modulus of elasticity. The method has the advantages of strong corrosion resistance of austenitic steel, good cold processing performance and strengthening of martensitic steel through heat treatment, and also has the defects of strong tissue sensitivity, large performance fluctuation, fast stress crack propagation, incorrect processing technology, easy generation of brittle fracture and the like. Therefore, the semi-austenitic precipitation hardening stainless steel has great difficulty in hot working or cold drawing, which is mainly characterized in that the plasticity of the material is seriously reduced when the production process is incorrect, the steel wire and the spring are easy to generate longitudinal cracks, and the stress crack tendency of the spring steel wire is great. At present, the more domestic materials are 0Cr17Ni7Al and 0Cr12Mn5Ni4Mo3Al stainless steel wires. According to the follow-up research on the market, the performance of the 0Cr17Ni7Al stainless steel wire greatly fluctuates when the wire is stored for a long time. After the wire is stored for 1 year, the phenomena of breakage, brittleness and incapability of winding springs occur to part of wires, the manufacturability is extremely poor, and the structure is unstable; the qualified rate of the 0Cr12Mn5Ni4Mo3Al stainless steel wire in spring pairing is about 90% when the stainless steel wire is newly put into a factory, and the qualified rate is reduced to 70% or even 50% after 1 year. Meanwhile, the strength of the two alloy wires is difficult to meet the more rigorous requirement, and the elasticity variance of the spring is large. Can not be stored for a long time at room temperature, is easy to generate stress release cracking, and has more strength grade reduction particularly at low temperature (-50 ℃). Therefore, a high-strength spring wire with high elastic modulus and good long-term stability is urgently needed, and contributes to electronic and electric appliances, food industry, chemical industry, textile machinery, automobile manufacturing, aviation national defense and the like.
Disclosure of Invention
The invention aims to provide a high-strength spring wire with high elastic modulus and a preparation method thereof, and solves the problems that the spring has large elasticity variance and cannot be stored for a long time at room temperature. The alloy wire has higher elastic modulus, excellent ultimate strength, torsion and winding performance reaching higher level under the conditions of room temperature and harsh environment (such as low temperature, high temperature and the like), and has good structure and performance stability when being stored for a long time.
The high-strength spring wire with high elastic modulus comprises the following chemical components in percentage by mass: c: less than or equal to 0.05 percent, Cr: 12.0% -17.0%, Ni: 5.0% -8.0%, Co: 3.0% -6.0%, Mo: 2.0% -3.0%, W: 1.5% -3.5%, Nb: 1.0% -2.0%, Al: 0.3% -0.5%, Ti: 0.3% -0.5%, Si: less than or equal to 0.3 percent, Mn: less than or equal to 0.3 percent, P: less than or equal to 0.01 percent, S: less than or equal to 0.01 percent, less than or equal to 0.005 percent of B, less than or equal to 0.05 percent of Ce, less than or equal to 0.01 percent of Zr, and the balance of iron.
The room-temperature elastic modulus of the high-strength spring wire is 195-214 GPa, the elastic modulus at 100 ℃ is 191-203 GPa, the elastic modulus at 200 ℃ is 177-190 GPa, and the elastic modulus at 300 ℃ is 168-185 GPa. The tensile strength at room temperature is 1900-2500 MPa, and the elongation is 1.0-5.0%; the low-temperature (-78 ℃) tensile strength is 1840-2420 MPa; after being placed for 2 years, the tensile ultimate strength of the alloy wire at room temperature changes by less than 5 percent, and the hardness changes by less than 4 percent.
A preparation method of a high-strength spring wire with high elastic modulus comprises the following specific steps and parameters:
1. taking raw materials according to the chemical component proportion of the alloy wire in percentage by mass, wherein C: less than or equal to 0.05 percent, Cr: 12.0% -17.0%, Ni: 5.0% -8.0%, Co: 3.0% -6.0%, Mo: 2.0% -3.0%, W: 1.5% -3.5%, Nb: 1.0% -2.0%, Al: 0.3% -0.5%, Ti: 0.3% -0.5%, Si: less than or equal to 0.3 percent, Mn: less than or equal to 0.3 percent, P: less than or equal to 0.01 percent, S: less than or equal to 0.01 percent, less than or equal to 0.005 percent of B, less than or equal to 0.05 percent of Ce, less than or equal to 0.01 percent of Zr, and the balance of iron.
The Fe element is one or more of pure iron, low-sulfur iron, ferrochrome, high-carbon ferrochrome, ferromolybdenum, ferrosilicon and ferromanganese;
the Cr element is one or more of ferrochrome, metallic chromium, brocade ferrochrome, low-nitrogen brocade ferrochrome and high-purity low-oxygen chromium;
the Mo element is one or more of metal molybdenum, ferromolybdenum and molybdenum-chromium rods;
the Ni element is one or more of electrolytic nickel, metallic nickel, gold nickel and high-purity nickel;
the Si element is one or more of high-carbon silicon, high-carbon ferrosilicon, high-purity polycrystalline silicon and metal silicon particles;
the Mn element is one or more of ferromanganese, metal manganese and electrolytic manganese sheets;
the Nb element is one or more of ferrocolumbium, smelted niobium and a high-purity polished niobium rod;
w element is one or more of ferrotungsten, tungsten rod and high-purity tungsten block;
the Al element is one or more of electrolytic aluminum, aluminum bar and pure aluminum strip;
the Ti element is one or more of a pure titanium rod, metallic titanium and sponge titanium;
co element is one or more of electrolytic cobalt, metallic cobalt and a Jinchuan cobalt plate;
ce element is one or more of metal cerium and high-purity cerium.
2. Mixing the raw materials according to a proportion, carrying out vacuum induction and vacuum consumable smelting, and then forging and hot rolling to a wire rod with phi 6-15 mm; in the cold drawing process, the deformation of the wire is controlled to be 50-65% in the cogging stage, the deformation of the intermediate blank is controlled to be 30-50% in the intermediate blank stage, and the deformation of the finished product is controlled to be 40-100%. The wire needs to be subjected to intermediate continuous annealing before cogging and intermediate blank cold drawing, the continuous annealing temperature is controlled to be 1000-1150 ℃, and the wire is subjected to hydrogen protection and rapid cooling; before cold drawing, dispersed phase uniform distribution heat treatment is carried out by matching with the deformation of the finished product, the wires are coiled for heat treatment, the heat treatment temperature is controlled to be 1050-1250 ℃, the temperature is kept for 60-120 minutes, and Ar gas or N is introduced2Gas protection, introducing high-pressure Ar gas or N into the furnace before discharging2The gas is cooled in the atmosphere. And (5) cold drawing the finished product after discharging. And winding the finished wire into a spring, and then carrying out heat preservation for 1-3 hours at 450-550 ℃.
The invention has the advantages that:
1. the high-strength spring wire with high elastic modulus and good long-term stability has the room-temperature elastic modulus of 195-214 GPa, the elastic modulus of 191-203 GPa at 100 ℃, the elastic modulus of 177-190 GPa at 200 ℃ and the elastic modulus of 168-185 GPa at 300 ℃. Powerful support is provided for the high-performance spring; the tensile strength at room temperature is 1900-2500 MPa, and the elongation is 1.0-5.0%. The low-temperature (-78 ℃) tensile strength is 1840 to 2420 MPa. The comprehensive performance reaches the advanced level in the world.
2. After the alloy wire is placed at room temperature for 2 years, the alloy structure is not obviously changed, the room-temperature tensile ultimate strength change of the alloy wire is less than 5%, and the hardness change is less than 4%. The alloy wire is aged for 1000 hours at 300 ℃, the change of the tensile strength is less than 2.7 percent, and the alloy wire is aged for 1000 hours at-78 ℃, and the change of the tensile strength is less than 2.0 percent. Under severe environment, the stability of the alloy wire reaches the world leading level.
3. The high-strength spring wire with high elastic modulus and good long-term stability has the advantages of simple preparation process, low cost, low requirement on equipment, convenience in production and development, good energy-saving effect and higher production efficiency. According to the proportion of alloy finished products, the prepared wire can be used for obtaining the spring wire with excellent performance and high elastic modulus and good long-term stability only by controlling the cold drawing deformation and the heat treatment process, and a large amount of energy can be saved.
Detailed Description
Example 1
The high-strength spring wire with high elastic modulus comprises the following chemical components in percentage by mass: c: 0.05%, Cr: 17.0%, Ni: 8.0%, Co: 6.0%, Mo: 3.0%, W: 3.5%, Nb: 2.0%, Al: 0.5%, Ti: 0.5%, Si: 0.3%, Mn: 0.3%, P: 0.01%, S: 0.01%, B: 0.005%, Ce: 0.05%, Zr: 0.01 percent, and the balance being iron.
Mixing pure iron, chromium metal and nickel metal and placing the mixture into the bottom of a crucible, and dispersedly loading molybdenum metal, niobium metal and tungsten metal on the middle upper part of the crucible. After mixing according to the proportion, forging the mixture after vacuum induction and vacuum consumable smelting, and hot rolling the mixture to a wire rod with the diameter of 6 mm. In the cold drawing process, the deformation of the wire is controlled at 50% in the cogging stage, 30% in the intermediate blank stage and 40% in the finished product. The wire needs to be subjected to intermediate continuous annealing before cogging and intermediate blank cold drawing, the continuous annealing temperature is controlled at 1000 ℃, and the wire is protected by hydrogen and rapidly cooled; carrying out dispersed phase uniform distribution heat treatment by matching with the deformation of the finished product before cold drawing of the finished product, forming wires into a disc for heat treatment, controlling the heat treatment temperature at 1050 ℃, keeping the temperature for 60 minutes, introducing Ar gas for protection, and introducing high-pressure Ar gas into the furnace for atmosphere cooling before discharging. And (5) cold drawing the finished product after discharging. And winding the finished wire into a spring, and then carrying out heat preservation for 1 hour at 450 ℃. The elastic modulus and linear expansion coefficient of the spring wire are shown in table 1. The ultimate strength stability of the spring wire under severe conditions is shown in table 2.
TABLE 1 coefficient of expansion and modulus of elasticity of the spring wire according to the invention
TABLE 2 measured values of the strength stability of the spring wire of the present invention under severe conditions
Example 2
The high-strength spring wire with high elastic modulus comprises the following chemical components in percentage by mass: c: 0.03%, Cr: 12.0%, Ni: 5.0%, Co: 3.0%, Mo: 2.0%, W: 1.5%, Nb: 1.0%, Al: 0.3%, Ti: 0.3%, Si: 0.2%, Mn: 0.2%, P: 0.005%, S: 0.005%, B: 0.00: 3%, Ce: 0.02%, Zr: 0.008% and the balance of iron.
Mixing pure iron, chromium metal and nickel metal and placing the mixture into the bottom of a crucible, and dispersedly loading molybdenum metal, niobium metal and tungsten metal on the middle upper part of the crucible. After mixing according to the proportion, forging the mixture after vacuum induction and vacuum consumable smelting, and hot rolling the mixture to a wire rod with the diameter of 15 mm. During cold drawing, the wire is deformed during the cogging stageThe amount is controlled to 65%, the intermediate blank stage is controlled to 50%, and the finished product deformation amount is controlled to 100%. The wire needs to be subjected to intermediate continuous annealing before cogging and intermediate blank cold drawing, the continuous annealing temperature is controlled at 1150 ℃, and the wire is subjected to hydrogen protection and quick cooling; performing dispersed phase uniform distribution heat treatment with deformation of the final product before cold drawing, coiling the wire material, performing heat treatment at 1250 deg.C for 120 min, introducing N2Gas protection, introducing high pressure N into the furnace before discharging2The gas is cooled in the atmosphere. And (5) cold drawing the finished product after discharging. Winding the finished wire into a spring, and then carrying out heat preservation for 3 hours at 550 ℃.
Example 3
The high-strength spring wire with high elastic modulus comprises the following chemical components in percentage by mass: c: 0.01%, Cr: 15.2%, Ni: 7.2%, Co: 4.8%, Mo: 2.8%, W: 2.9%, Nb: 1.5%, Al: 0.4%, Ti: 0.4%, Si: 0.1%, Mn: 0.1%, P: 0.001%, S: 0.001%, B: 0.002%, Ce: 0.02%, Zr: 0.005% and the balance of iron.
Mixing pure iron, chromium metal and nickel metal and placing the mixture into the bottom of a crucible, and dispersedly loading molybdenum metal, niobium metal and tungsten metal on the middle upper part of the crucible. After mixing according to the proportion, forging is carried out after vacuum induction and vacuum consumable smelting, and hot rolling is carried out until the wire rod with the diameter of 10mm is obtained. In the cold drawing process, the deformation of the wire is controlled to be 55 percent in the cogging stage, 40 percent in the intermediate blank stage and 80 percent in the finished product. The wire needs to be subjected to intermediate continuous annealing before cogging and intermediate billet cold drawing, the continuous annealing temperature is controlled at 1100 ℃, and the wire is protected by hydrogen and rapidly cooled; carrying out disperse phase uniform distribution heat treatment by matching with the deformation of the finished product before cold drawing of the finished product, forming wires into a disc for heat treatment, controlling the heat treatment temperature at 1200 ℃, keeping the temperature for 100 minutes, introducing Ar gas for protection, and introducing high-pressure Ar into the furnace for atmosphere cooling before discharging. And (5) cold drawing the finished product after discharging. And winding the finished wire into a spring, and then carrying out heat preservation for 2 hours at 500 ℃.
In conclusion, by properly adding alloying elements such as Co, Ni and Mo, the problems of strong tissue sensitivity, large performance fluctuation, low elastic modulus, fast stress crack propagation, incorrect processing technology, easy brittle fracture and the like of the spring wire in the prior art are solved, and particularly the problems of material performance reduction and long-term service stability in extreme environments are solved. Thereby providing the spring wire which is used for harsh environment and has simple operation, low cost and excellent comprehensive performance. The spring part is widely applied, not only can be applied to spring parts with large environmental change and high load in service under extreme environment, but also can be applied to other parts which require the spring parts to be used for tanks, armored vehicles, large-scale transport vehicles, airplane umbrella doors and the like with strict low-temperature environment requirements and high toughness matching.
Finally, it should be noted that: the above embodiments are only used to illustrate the present invention and do not limit the technical solutions described in the present invention; thus, although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted; all such modifications and variations are intended to be included herein within the scope of this disclosure and the appended claims.
Claims (2)
1. The high-strength spring wire with high elastic modulus is characterized by comprising the following chemical components in percentage by mass: c: less than or equal to 0.05 percent, Cr: 12.0% -17.0%, Ni: 5.0% -8.0%, Co: 3.0% -6.0%, Mo: 2.0% -3.0%, W: 1.5% -3.5%, Nb: 1.0% -2.0%, Al: 0.3% -0.5%, Ti: 0.3% -0.5%, Si: less than or equal to 0.3 percent, Mn: less than or equal to 0.3 percent, P: less than or equal to 0.01 percent, S: less than or equal to 0.01 percent, less than or equal to 0.005 percent of B, less than or equal to 0.05 percent of Ce, less than or equal to 0.01 percent of Zr, and the balance of iron;
the room-temperature elastic modulus of the high-strength spring wire is 195-214 GPa, the elastic modulus at 100 ℃ is 191-203 GPa, the elastic modulus at 200 ℃ is 177-190 GPa, and the elastic modulus at 300 ℃ is 168-185 GPa; the tensile strength at room temperature is 1900-2500 MPa, and the elongation is 1.0-5.0%; the tensile strength at the low temperature of minus 78 ℃ is 1840 to 2420 MPa; after being placed for 2 years, the tensile ultimate strength of the alloy wire at room temperature changes by less than 5 percent, and the hardness changes by less than 4 percent.
2. The preparation method of the high-strength spring wire with high elastic modulus is characterized by comprising the following specific steps and parameters:
1) taking raw materials according to the chemical component proportion of the alloy wire in percentage by mass, wherein C: less than or equal to 0.05 percent, Cr: 12.0% -17.0%, Ni: 5.0% -8.0%, Co: 3.0% -6.0%, Mo: 2.0% -3.0%, W: 1.5% -3.5%, Nb: 1.0% -2.0%, Al: 0.3% -0.5%, Ti: 0.3% -0.5%, Si: less than or equal to 0.3 percent, Mn: less than or equal to 0.3 percent, P: less than or equal to 0.01 percent, S: less than or equal to 0.01 percent, less than or equal to 0.005 percent of B, less than or equal to 0.05 percent of Ce, less than or equal to 0.01 percent of Zr, and the balance of iron;
the Fe element is one or more of pure iron, low-sulfur iron, ferrochrome, high-carbon ferrochrome, ferromolybdenum, ferrosilicon and ferromanganese;
the Cr element is one or more of ferrochrome, metallic chromium and high-purity low-oxygen chromium;
the Mo element is one or more of metal molybdenum, ferromolybdenum and molybdenum-chromium rods;
the Ni element is one or more of electrolytic nickel, metallic nickel, gold nickel and high-purity nickel;
the Si element is one or more of high-carbon silicon, high-carbon ferrosilicon, high-purity polycrystalline silicon and metal silicon particles;
the Mn element is one or more of ferromanganese, metal manganese and electrolytic manganese sheets;
the Nb element is one or more of ferrocolumbium, smelted niobium and a high-purity polished niobium rod;
w element is one or more of ferrotungsten, tungsten rod and high-purity tungsten block;
the Al element is one or more of electrolytic aluminum, aluminum bar and pure aluminum strip;
the Ti element is one or more of a pure titanium rod, metallic titanium and sponge titanium;
co element is one or more of electrolytic cobalt, metallic cobalt and a Jinchuan cobalt plate;
ce element is one or more of metal cerium and high-purity cerium;
2) mixing the raw materials according to a proportion, carrying out vacuum induction and vacuum consumable smelting, and then forging and hot rolling to a wire rod with phi 6-15 mm; in the cold drawing process, the deformation of the wire is controlled to be 50-65% in the cogging stage, and the middle part isThe blank stage is controlled to be 30-50%, and the deformation of the finished product is controlled to be 40-100%; the wire needs to be subjected to intermediate continuous annealing before cogging and intermediate blank cold drawing, the continuous annealing temperature is controlled to be 1000-1150 ℃, and the wire is subjected to hydrogen protection and rapid cooling; before cold drawing, dispersed phase uniform distribution heat treatment is carried out by matching with the deformation of the finished product, the wires are coiled for heat treatment, the heat treatment temperature is controlled to be 1050-1250 ℃, the temperature is kept for 60-120 minutes, and Ar gas or N is introduced2Gas protection, introducing high-pressure Ar gas or N into the furnace before discharging2Cooling the gas in the atmosphere; taking out the product from the furnace and performing cold drawing on the finished product; and winding the finished product wire into a spring, and then carrying out heat preservation for 1-3 hours at 450-550 ℃.
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| CN112742883B (en) * | 2019-10-31 | 2022-10-21 | 丹阳亿鑫合金有限公司 | Preparation method of high-temperature-resistant and oxidation-resistant nickel-based alloy spring wire |
| CN111485092B (en) * | 2020-06-01 | 2021-04-30 | 嘉善永鑫紧固件有限公司 | Elastic gasket and preparation method and application thereof |
| CN111705273A (en) * | 2020-07-30 | 2020-09-25 | 北京北冶功能材料有限公司 | High-strength spring foil strip and preparation method thereof |
| CN114410896B (en) * | 2022-01-27 | 2022-10-21 | 北京科技大学 | Ultrahigh-strength medium-carbon spring steel, heat treatment process and high-speed train bogie spring |
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