CN113737091A - Steel for low-magnetism high-strength corrosion-resistant fastener and fastener - Google Patents
Steel for low-magnetism high-strength corrosion-resistant fastener and fastener Download PDFInfo
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Abstract
The steel for the low-magnetism high-strength corrosion-resistant fastener comprises the following chemical components in percentage by mass: less than or equal to 0.05%, Si: less than or equal to 1 percent, Mn: 5-8%, S is less than or equal to 0.03%, P is less than or equal to 0.03%, Cr: 19-24%, Ni: 14-17%, Mo: 2-4%, N: 0.2 to 0.4%, the balance being Fe and unavoidable impurities, a pitting equivalent index PREN of not less than 32, PREN = (Cr +3.3 Mo + 16N). The invention selects the high Cr, high Ni and high N austenitic stainless steel material, improves the N solubility and the strain hardening index of the material by adding certain Mn element, and improves the matrix strength of the solid solution material by N alloying. The structural stability of the material in the cold deformation strengthening process is realized through the reasonable matching of Cr, Ni, Mo, Mn and N, the formation of deformation induced martensite is avoided, and the magnetic performance of the material in a cold deformation high-strength state is at an extremely low level. Simultaneously, through the higher strain hardening index of the material, the crushing and the occlusion of the contact surface of the threaded connection pair of the fastening piece are avoided, the anti-occlusion performance of the material is effectively improved, and the fastening piece can effectively avoid the occlusion in the screwing process through simple lubrication.
Description
Technical Field
The invention relates to the field of high-strength stainless steel fasteners, in particular to steel for a low-magnetism high-strength corrosion-resistant fastener and the fastener.
Background
The existing stainless steel corrosion resistant fastener can be divided into austenitic stainless steel, ferritic stainless steel, martensitic stainless steel, duplex stainless steel, precipitation hardening stainless steel and the like according to the tissue types. Among various stainless steels, ferritic stainless steel is influenced by lower strength and low-temperature impact toughness, and is difficult to meet the engineering application requirements of high-strength fasteners; although martensitic stainless steel and precipitation hardening stainless steel have high strength, the structure is alpha-Fe structure, so the magnetic property is strong, and the low-magnetic property application occasion cannot be met. Low Cr and Mo content, poor corrosion resistance and incapability of meeting the requirements of severe corrosion environments, such as oceans and the like containing Cl-And (4) environment. For the cathodic protection environment, the high-strength martensite and precipitation hardening stainless steel are easy to be hydrogen-embrittled due to cathodic over-protection, and have poor adaptability; although the duplex stainless steel has excellent corrosion resistance, the forming performance of the material is poor due to the structure of gamma + alpha structure, and the duplex stainless steel is not suitable for the forming process of large-scale complex fasteners. Meanwhile, the material has higher magnetism because of containing about 50% of alpha phase. In the cathodic protection environment, similar to martensite and precipitation hardening stainless steel, hydrogen embrittlement caused by cathodic over-protection is easy to occur under the influence of alpha phase structure, and the requirements of underwater application, low magnetism application and other application occasions are difficult to meet.
The austenitic stainless steel has good formability and corrosion resistance, is commonly used steel for corrosion-resistant stainless steel fasteners, is commonly used as a material such as A2, A3, A4, A5 and the like in GB/T3098.6 standard, is influenced by material components and solid solution state strength, and is difficult to reach the strength level of 1000MPa, generally 700MPa and 800MPa even after cold deformation. Although the A2 and A3 materials can obtain the strength level of more than 1000MPa through large deformation cold deformation, the magnetism of the materials is rapidly improved under the influence of deformation induced phase change, the stress corrosion resistance of the materials is seriously deteriorated, and the application requirement of the materials in a severe corrosion environment cannot be met. Meanwhile, the materials such as A2, A3, A4 and A5 have low overall corrosion resistance, and have certain defects in stress corrosion resistance in marine environment, particularly in high-temperature environment such as steam system and deck system.
In the case of cold-work hardened austenitic stainless steel, as the material specification increases, the cold deformation non-uniformity increases, and for example, the strength of the material in a solid solution state is low, and the cold deformation and the overall strength are difficult to reach a high strength level. In the existing materials for large-size corrosion-resistant high-strength fasteners, the materials mainly adopted for the requirements of lower corrosion resistance are precipitation hardening stainless steel such as 05Cr17Ni4Cu4Nb, 0Cr16Ni5Mo and the like and super martensitic stainless steel. For high corrosion resistance, nickel-based or iron-nickel-based age-hardening alloys, such as Incoloy925, Incoloy945, Inconel718, Inconel X750, are generally selected. All the materials need to be strengthened through heat treatment, the manufacturing process is complex, the cost is high, and the large-scale batch cold heading manufacturing is difficult to meet. But the stainless steel material for the large-specification high-strength fastener has the advantages of low cost, good processing performance, excellent corrosion resistance and low magnetism. .
Chinese patent CN 111118411 a discloses a high strength stainless steel, which can obtain strength over 1000MPa, but after solution treatment, the material is austenite and martensite dual-phase structure, and contains high-temperature ferrite with high content, and simultaneously, the material has low content of Cr, Mo and N, so the magnetic property and corrosion resistance of the material are all at low level; application patent 201911402733.7 discloses a nickel-free non-magnetic high-strength stainless steel having extremely high Mn content and Co content, which can achieve tensile strength close to 900MPa and extremely low magnetism, but the Cr content of the material is low, and the material does not contain Mo element which is extremely beneficial to local corrosion resistance, so that the material can not reach the level of the material of the invention in strength and corrosion resistance; application patent 201911401718.0 discloses a quenching and tempering process for high-strength stainless steel fasteners, which comprises quenching and tempering heat treatment, has no relevant description on materials, and does not conform to the heat treatment process specification of common austenitic stainless steel; the patent application: 201910397923.8 discloses a high strength stainless steel fastener, but the patent only discloses the structural details of the fastener and there is no relevant description of the stainless steel material and the associated properties.
Meanwhile, the existing general stainless steel fastener is generally disturbed by occlusion and scratch in the screwing and tightening process, the normal construction pre-tightening and disassembly of the stainless steel fastener are seriously influenced, in order to ensure good application performance, the problem that the important application occasions are usually solved by adopting lubricating layers such as electro-coppering, silver or fluoroplastic coating and the like is solved, and the cost and the manufacturing period of the fastener are seriously increased.
Disclosure of Invention
In order to solve the technical problems, the invention provides the steel for the low-magnetism high-strength corrosion-resistant fastener and the fastener. The structural stability of the material in the cold deformation strengthening process is realized through the reasonable matching of Cr, Ni, Mo, Mn and N, the formation of deformation induced martensite is avoided, and the magnetic performance of the material in a cold deformation high-strength state is at an extremely low level. Simultaneously, through the higher strain hardening index of the material, the crushing and the occlusion of the contact surface of the threaded connection pair of the fastening piece are avoided, the anti-occlusion performance of the material is effectively improved, and the fastening piece can effectively avoid the occlusion in the screwing process through simple lubrication.
In order to realize the technical purpose, the adopted technical scheme is as follows: the steel for the low-magnetism high-strength corrosion-resistant fastener comprises the following chemical components in percentage by mass: less than or equal to 0.05%, Si: less than or equal to 1 percent, Mn: 5-8%, S is less than or equal to 0.03%, P is less than or equal to 0.03%, Cr: 19-24%, Ni: 14-17%, Mo: 2-4%, N: 0.2 to 0.4%, the balance being Fe and unavoidable impurities, a pitting equivalent index PREN of not less than 32, PREN = (Cr +3.3 Mo + 16N).
The content relation of the materials C, Si, Cr, Ni, Mo, Mn and N needs to satisfy: mn + Ni + Si +1.5Cr +2Mo +47(C + N) is not less than 69.
The relationship between Ni and Mn of the material needs to satisfy: 1 is less than or equal to 3 and Mn-Ni is less than or equal to 7.
A fastener is smelted by adopting low-carbon austenitic stainless steel material general smelting process equipment or is refined and remelted by adopting an electroslag secondary refining process to obtain a smelting material of the steel for the low-magnetic high-strength corrosion-resistant fastener as claimed in any one of claims 1 to 3;
directly casting the smelting material into an ingot or a continuous casting blank, and performing a hot forming process to obtain a bar material;
keeping the temperature of a rolled or forged rod material at 1020-1100 ℃ for solid solution, discharging the rod material from a furnace, quickly cooling the rod material to below 400 ℃,
the bar stock is deformed by cold drawing within 40 percent to obtain the anti-occlusion high-strength corrosion-resistant fastener with the relative magnetic conductivity less than 1.05 and the tensile strength more than or equal to 1000 MPa.
The invention has the beneficial effects that: through component optimization and adjustment and a reasonable deformation strengthening process, the structural stability, the strength and the seizure resistance of the austenitic stainless steel are effectively improved, and the manufacture of large-size, high-strength, low-magnetism and seizure-resistant corrosion-resistant fasteners is realized. The manufacturing method can realize the manufacturing of the anti-seizure high-strength fastener with the specification of less than or equal to 39, the relative magnetic conductivity of less than 1.05 and the tensile strength of more than or equal to 1000MPa, and the achievement material can also be used in a solid solution state and also has higher strength and mechanical property compared with the common austenitic stainless steel.
Drawings
FIG. 1 is a typical structure diagram of the solid solution state of the stainless steel of the present invention.
Detailed Description
The steel for the corrosion-resistant high-strength fastener comprises the following chemical components in percentage by mass: less than or equal to 0.05%, Si: less than or equal to 1 percent, Mn: 5-8%, S is less than or equal to 0.03%, P is less than or equal to 0.03%, Cr: 19-24%, Ni: 14-17%, Mo: 2-4%, N: 0.2 to 0.4 percent, the balance being Fe and inevitable impurities, a pitting equivalent index PREN not less than 34, PREN = (Cr +3.3 Mo + 16N).
The content relation of the materials C, Si, Cr, Ni, Mo, Mn and N needs to satisfy: mn + Ni + Si +1.5Cr +2Mo +47(C + N) is not less than 69.
The relationship between Ni and Mn of the material needs to satisfy: 1 is less than or equal to 3 and Mn-Ni is less than or equal to 7.
The main alloy element content and the function of the material are as follows:
1) c element: the selection of the content of C (less than or equal to 0.05%) is an important element influencing the corrosion resistance of the stainless steel, the C has higher solubility in the solid solution state of the austenitic stainless steel, and the solution forms along-crystal carbide precipitation in the processes of sensitization and the like, thereby seriously deteriorating the corrosion resistance of the material. In view of corrosion resistance, the lower the C content, the better, but the too low C content is affected by the carbon-oxygen reaction balance, which has higher requirements for the smelting process or the charging material, resulting in a sharp increase in the manufacturing cost of the material, therefore, the too low C content is not suitable. C exists in a solid solution state in the material for the content of C below 0.03 percent, so that the material is ensured to have excellent corrosion resistance. C belongs to elements for obviously strengthening the strength of austenitic stainless steel, but C solid solution strengthening is not selected as a material core strengthening means in the invention in consideration of the corrosion resistance of the material. The C content should be controlled at a low level as required by the process operation. Meanwhile, considering that the high-strength fastener has low sensitization possibility in the use process, the C content with proper technological performance can be selected on the premise of excellent intergranular corrosion resistance, so that decarburization operation in the smelting process is facilitated, decarburization time is shortened, energy consumption is saved, and smelting cost is reduced;
2) si element: the Si element is used as an inevitable alloy element in common ferroalloy furnace charge and stainless steel return, can effectively improve the corrosion resistance of the material in an oxidizing environment, and has certain strengthening effect in austenitic stainless steel due to the larger atomic size difference with Fe element, so that the Si content is not suitable to be too low. But the Si element has obvious effect of promoting the precipitation of harmful phases such as sigma phase and the like, and in order to avoid the precipitation of the harmful phases such as sigma phase and the like, the content of the Si element is selected to be controlled to be less than or equal to 1 percent, and is more preferable in the range of 0.3-1 percent;
3) mn element: mn can effectively improve the solubility of N, improve the austenite stability of the stainless steel, and simultaneously can effectively improve the strain hardening index of the material and improve the seizure resistance of the material. However, Mn adversely affects the corrosion resistance of stainless steel materials, resulting in deterioration of the local corrosion resistance of the materials. Therefore, on the basis of fully considering Mn to N alloying and Mn improving the anti-seizure performance of the material, the Mn is controlled to be in a proper level, and the content of Mn element is controlled to be 5-8%, preferably 6-8%;
4) cr element: cr element belongs to a key element for forming a stainless steel passive film and determines the corrosion resistance of the stainless steel. Therefore, the invented material must ensure a sufficient Cr content, and the Cr content is controlled to a high level. However, the Cr content is not necessarily too high in consideration of the precipitation of the harmful phase sigma phase and the Laves phase of the material, the manufacturing cost of the material, the manufacturability and the balance with elements such as Ni and Mn. The content of Cr element is controlled to be 19-24%, preferably 20-22%;
5) mo element: the Mo element can effectively improve the forming capability of the passive film made of the stainless steel material and the repairing capability of the damaged passive film, and is an important element for improving the local corrosion resistance of the material. However, the solubility of Mo in stainless steel materials is limited, so that the formation of intermetallic compounds is easily promoted, and the high Mo alloy content causes the deterioration of the processing performance of the materials. Therefore, the content of Mo in the material of the invention is selected to be 2.0-4.0%, preferably 2.5-3.5%, and based on proper process control, the material of the invention can also extend the content of Mo to a higher level to obtain more excellent corrosion resistance, but need to avoid the precipitation of high-temperature ferrite;
6) ni element: ni is an important element for forming stable austenite, can effectively improve the solubility of Cr and Mo alloy elements of the material, slow or avoid the precipitation of intermetallic compounds, and is an important alloy element for balancing the components of the material. In order to improve the corrosion resistance of the material, high alloy elements of Cr and Mo are added into the material, so that a sufficient amount of Ni element needs to be added to balance the components of the material, but the Ni content is not too high, on one hand, the too high Ni content can sharply increase the manufacturing cost of the material, the beneficial effect on the corrosion resistance of the material is limited, and on the other hand, the too high Ni content can cause the strain hardening index of the material to be reduced, and the seizure resistance of the material to be reduced. Therefore, the content of the Ni element in the material is selected to be 14-17%, preferably 15-17%;
7) n element: n belongs to the main strengthening elements of the material, and can effectively improve the solid solution state matrix strengthening of the material. Simultaneously N can effectively improve the stability of austenite and the corrosion resistance of the materialCan be used. However, the alloying process of N is influenced by the solubility of N in the material on the one hand, and on the other hand, the lower N content can be used2The gas alloying can be economically realized in smelting, if the high N content is adopted, the processes of ferrochromium nitride, pressurized nitrogen blowing and the like are adopted, so that the production and smelting cost is greatly increased, and the risk of nitrogen holes in the material is increased. The balance of bonding strength control and component design, the content of N element in the material is selected to be 0.2-0.4%, preferably 0.25-0.35%;
8) in order to ensure that the material has enough excellent corrosion resistance which is superior to the level of 316L material, the pitting equivalent index PREN of the material is more than or equal to 32;
9) in order to avoid ferrite structure of the material and martensite phase transformation in the subsequent cold deformation strengthening process, the content relationship of the material C, Si, Cr, Ni, Mo, Mn and N of the invention needs to satisfy: mn + Ni + Si +1.5Cr +2Mo +47(C + N) is not less than 69.
10) In order to ensure that the material has good seizure resistance and higher strain hardening index, and meanwhile, considering the local corrosion resistance of the material, the relationship between Ni and Mn of the material needs to satisfy: 7 is more than or equal to 3 and Mn-Ni is more than or equal to 1.
The material is influenced by the content of alloy elements, the dissolution temperature of precipitated phases is different, the content of C is less than 0.05 percent, and the dissolution of the precipitated phases can be ensured by solid solution at 1020 ℃. The high-temperature solution treatment can ensure the dissolution of a precipitated phase of the material to form a uniform austenite structure, but the excessive high-temperature solution treatment can cause coarse material grains and reduce the area of a grain boundary, so that the corrosion resistance of the material is not improved. Therefore, the solid solution temperature of the material is selected to be 1020-1100 ℃. The temperature range can ensure the full dissolution of precipitated phases and simultaneously can not cause the rapid coarsening of crystal grains of the material. As shown in fig. 1, the material has an austenite structure as seen from the structure.
The material of the invention needs to ensure the sufficient dissolution of harmful precipitated phases through solution treatment so as to ensure the corrosion resistance of the material, and simultaneously, the strength of the material is improved through cold deformation strengthening after solution treatment so as to ensure that the strength of the material reaches the technical index strength level, and in order to avoid the reduction of the corrosion resistance of the material caused by the precipitation of deformation induced martensite and excessive deformation, the cold deformation of the material is controlled within 40 percent.
The preparation process of the stainless steel material comprises the following steps:
the material can be smelted by adopting common smelting process equipment for common low-carbon austenitic stainless steel materials, such as: the smelting process of medium frequency induction, electric furnace + AOD, electric furnace + VOD and the like, and the secondary refining process of electroslag and the like can also be adopted for refining and remelting.
The smelting material can be directly cast into an ingot or a continuous casting billet, and then hot forming processes such as rolling, forging and the like are carried out.
And (3) preserving heat and dissolving the rolled or forged and formed bar stock at 1020-1100 ℃, and discharging and quickly cooling the bar stock to below 400 ℃.
The bar stock is deformed by cold drawing within 40 percent to obtain the required strength, and the required high-strength fastener can be obtained by controlling the cold deformation within 40 percent by combining with the cold heading fastener process.
The material manufacturing process flow is implemented as follows:
the material smelting furnace charge is selected from 304, 2205 and other stainless steel returns, scrap steel, high-carbon ferrochrome, ferromolybdenum, electrolytic manganese, electrolytic nickel, crystalline silicon, temperature-raising material aluminum ingots and the like; the slagging material is selected from: lime, and the like.
The method comprises the steps of smelting steel by adopting medium-frequency induction, slagging by lime, drawing slag after molten steel is melted down and tapping, adding the molten steel into an AOD furnace for refining, slagging, blowing nitrogen and oxygen for decarburization, adding crystalline silicon for reduction, alloying Mn, and adjusting the content of N by utilizing nitrogen and argon switching according to the analysis result in front of the furnace. Tapping and pouring after the components hit the target components. The tapping temperature is 1550-1590 ℃. And casting into 1.5T electrode rods after the sedation.
And remelting the electrode into an electroslag ingot with the specification of 1.5T by adopting an electroslag remelting process.
Heating the electroslag ingot, cogging and forging to 150 × 150 square, sawing and rolling to form phi 42 round bars. Respectively adopting 1020 ℃ and 1080 ℃ to carry out solution treatment.
And (3) carrying out acid pickling drawing on the bar stock after the solution treatment, and testing the mechanical property, the corrosion property and the magnetic property of the material.
TABLE 1 chemical composition of inventive Steel examples
TABLE 2 test results of mechanical, corrosion and magnetic properties of the inventive steels
Claims (4)
1. A low-magnetism high-strength corrosion-resistant fastener steel is characterized in that: the chemical components comprise the following components in percentage by mass: less than or equal to 0.05%, Si: less than or equal to 2 percent, Mn: 5-8%, S is less than or equal to 0.03%, P is less than or equal to 0.03%, Cr: 19-24%, Ni: 14-17%, Mo: 2-4%, N: 0.2 to 0.4%, the balance being Fe and unavoidable impurities, a pitting equivalent index PREN of not less than 32, PREN = (Cr +3.3 Mo + 16N).
2. The steel for a low-magnetic high-strength corrosion-resistant fastener according to claim 1, wherein: the content relation of the materials C, Si, Cr, Ni, Mo, Mn and N needs to satisfy: mn + Ni + Si +1.5Cr +2Mo +47(C + N) is not less than 69.
3. The steel for a low-magnetic high-strength corrosion-resistant fastener according to claim 1, wherein: the relationship between Ni and Mn of the material needs to satisfy: 1 is less than or equal to 3 and Mn-Ni is less than or equal to 7.
4. A fastener, characterized by: smelting by adopting general smelting process equipment for low-carbon austenitic stainless steel materials or refining and remelting by adopting an electroslag secondary refining process to obtain a smelting material of the steel for the low-magnetic high-strength corrosion-resistant fastener as claimed in any one of claims 1 to 3;
directly casting the smelting material into an ingot or a continuous casting blank, and performing a hot forming process to obtain a bar material;
keeping the temperature of a rolled or forged rod material at 1020-1100 ℃ for solid solution, discharging the rod material from a furnace, quickly cooling the rod material to below 400 ℃,
the bar stock is deformed by cold drawing within 40 percent to obtain the anti-occlusion high-strength corrosion-resistant fastener with the relative magnetic conductivity less than 1.05 and the tensile strength more than or equal to 1000 MPa.
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Cited By (5)
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| CN114574778A (en) * | 2022-03-04 | 2022-06-03 | 中国原子能科学研究院 | Alloying method for improving liquid lead bismuth corrosion resistance of high-performance fastener for lead-based reactor |
| CN114657465A (en) * | 2022-03-04 | 2022-06-24 | 中国科学院金属研究所 | Alloying method for improving stress relaxation resistance of high-performance fastener for lead-based pile |
| CN115466909A (en) * | 2022-10-26 | 2022-12-13 | 浦项(张家港)不锈钢股份有限公司 | Austenitic stainless steel, preparation process and application |
| CN116083819A (en) * | 2023-03-20 | 2023-05-09 | 杭州铭赫科技有限公司 | High-strength austenitic stainless steel powder and preparation method thereof |
| CN118207471A (en) * | 2024-05-20 | 2024-06-18 | 成都先进金属材料产业技术研究院股份有限公司 | Preparation method of hydrogen-resistant stainless steel master alloy bar and hydrogen storage container |
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| CN108866419A (en) * | 2018-06-21 | 2018-11-23 | 洛阳双瑞特种装备有限公司 | A kind of high intensity high corrosion resistance austenitic stainless steel and preparation method thereof |
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