CN112143973B - High-strength high-corrosion-resistance super austenitic stainless steel and preparation method thereof - Google Patents
High-strength high-corrosion-resistance super austenitic stainless steel and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the field of stainless steel, and particularly provides high-strength high-corrosion-resistance super austenitic stainless steel and a preparation method thereof. The invention relates to high-strength high-corrosion-resistance super austenitic stainless steel, which comprises the following components in percentage by weight: 0.01 to 0.03 percent of C, 0.3 to 0.7 percent of Si, 1 to 2.5 percent of Mn, less than or equal to 0.040 percent of P, less than or equal to 0.004 percent of S, 21 to 24 percent of Cr, 17 to 20 percent of Ni, 4.5 to 6 percent of Mo, 0.5 to 2.5 percent of W, 1 to 2.5 percent of Cu, 0.1 to 0.4 percent of Nb, 0.05 to 0.25 percent of V, 0.1 to 0.4 percent of Ti, 0.3 to 0.7 percent of Co, 0.23 to 0.3 percent of N, 0.001 to 0.005 percent of B, 0.005 to 0.03 percent of Ce, and the balance of Fe and other inevitable impurity elements. The high-strength high-corrosion-resistance super austenitic stainless steel has excellent room-temperature mechanical property, high-temperature yield strength and corrosion resistance.
Description
Technical Field
The invention belongs to the field of stainless steel, and particularly provides high-strength high-corrosion-resistance super austenitic stainless steel and a preparation method thereof, which are suitable for materials for high-end equipment in the fields of petrifaction, environmental protection and paper making.
Background
The equipment manufacturing industry is used as a basic and strategic industry for the development of economic society, and the development level and the modernization degree determine the industrial competitiveness and the comprehensive strength of a country or a region. With the upgrading and upgrading of equipment such as petrifaction, environmental protection, papermaking and the like, the service environment of materials is increasingly severe, and the materials face harsh environments such as high acid, high sulfur, chloride ions, high temperature, high pressure and the like, so that higher requirements are provided for the performances such as corrosion resistance, strength and the like of stainless steel materials. The existing traditional austenitic stainless steel cannot completely meet the requirements, and the problems of seam corrosion, point corrosion, stress corrosion and the like can occur in the using process, so that the caused equipment damage problem becomes serious day by day, the emergency shutdown or sudden accident of the device is easily caused, and the serious loss is caused to the security of life and property. The super austenitic stainless steel is used as a key material urgently needed by the advanced equipment manufacturing industry, has high strength and toughness and excellent pitting corrosion resistance, crevice corrosion resistance and stress corrosion resistance, can be widely applied to extremely harsh service environments, and is a key material for continuing the high-end equipment manufacturing industry in China.
The super austenitic stainless steel products which are widely applied at present mainly comprise 904L, S31254, N08367, N08926 and the like. However, in the early stage of the design, mainly from the viewpoint of improving corrosion resistance, the steel grade improves the uniform corrosion resistance by reducing the carbon content and improving the Cr content, improves the pitting corrosion resistance and the crevice corrosion resistance by adding 4 to 6 percent of Mo and less than 1.5 percent of Cu, and simultaneously improves the Ni content by a proper amount and adds 0.1 to 0.2 percent of N to stabilize the austenite structure. The above conventional materials have the following problems in application:
(1) because the material is lack of strengthening elements, the strength is generally not high, and particularly the high-temperature resistant yield strength and the creep resistance are poor. With the upgrade of high-end equipment, the service temperature of many parts is higher and higher, the bearing pressure is higher and higher, and simultaneously, the corrosion conditions are still harsh, the corrosion environment cannot be met by selecting heat-resistant steel, and the strength of selecting super austenitic stainless steel is not enough. The strength of 654SMO of the super austenitic stainless steel with higher Mo content (7%) and ultrahigh N content (0.5%) is improved to a certain extent, but the industrial mass production is difficult due to the overhigh N content;
(2) due to high Mo content, a large amount of harmful sigma phase is easily precipitated in the material, the sigma phase is coarsened and grown in the long-term service process, the impact toughness of the material is greatly reduced, and meanwhile, the structure stability is poor, so that the failure risk in long-term use is suddenly increased;
(3) the low grain boundary strength leads to poor hot working performance, surface crack defects are easy to generate in the production and preparation process, and the production and manufacturing cost is high.
For the above reasons, only expensive nickel-based alloys can be selected at present in more severe service environments. Therefore, there is a need to develop a super austenitic stainless steel having both high strength and high corrosion resistance.
Disclosure of Invention
The invention aims to provide high-strength high-corrosion-resistance super austenitic stainless steel and a preparation method thereof, which solve the problems of low strength, poor structure stability, poor corrosion resistance and the like of the existing material and meet the use requirements of key materials under severe service conditions of high-end equipment in the fields of petrifaction and the like.
On one hand, the invention provides high-strength and high-corrosion-resistance super austenitic stainless steel, which comprises the following components in percentage by weight: 0.01 to 0.03 percent of C, 0.3 to 0.7 percent of Si, 1 to 2.5 percent of Mn, less than or equal to 0.040 percent of P, less than or equal to 0.004 percent of S, 21 to 24 percent of Cr, 17 to 20 percent of Ni, 4.5 to 6 percent of Mo, 0.5 to 2.5 percent of W, 1 to 2.5 percent of Cu, 0.1 to 0.4 percent of Nb, 0.05 to 0.25 percent of V, 0.1 to 0.4 percent of Ti, 0.3 to 0.7 percent of Co, 0.23 to 0.3 percent of N, 0.001 to 0.005 percent of B, 0.005 to 0.03 percent of Ce, and the balance of Fe and other inevitable impurity elements.
The high-strength high-corrosion-resistance super austenitic stainless steel comprises the following components in percentage by weight: 0.015 to 0.03 percent of C, 0.4 to 0.7 percent of Si, 1 to 2 percent of Mn, less than or equal to 0.035 percent of P, less than or equal to 0.003 percent of S, 22 to 24 percent of Cr, 17 to 19 percent of Ni, 5 to 6 percent of Mo, 0.5 to 2 percent of W, 1 to 2 percent of Cu, 0.1 to 0.3 percent of Nb, 0.05 to 0.2 percent of V, 0.1 to 0.3 percent of Ti, 0.3 to 0.6 percent of Co, 0.23 to 0.28 percent of N, 0.001 to 0.004 percent of B, 0.005 to 0.02 percent of Ce, and the balance of Fe and other inevitable impurity elements.
The high-strength high-corrosion-resistance super austenitic stainless steel comprises the following components in percentage by weight: 0.02 to 0.03 percent of C, 0.4 to 0.6 percent of Si, 1 to 1.5 percent of Mn, less than or equal to 0.03 percent of P, less than or equal to 0.002 percent of S, 22 to 23 percent of Cr, 18 to 19 percent of Ni, 5 to 5.5 percent of Mo, 1 to 2 percent of W, 1.5 to 2 percent of Cu, 0.2 to 0.3 percent of Nb, 0.1 to 0.2 percent of V, 0.2 to 0.3 percent of Ti, 0.4 to 0.6 percent of Co, 0.25 to 0.28 percent of N, 0.002 to 0.004 percent of B, 0.01 to 0.02 percent of Ce, and the balance of Fe and other inevitable impurity elements.
The high-strength and high-corrosion-resistance super austenitic stainless steel has the advantages that Nb + V + Ti is less than or equal to 1 percent, Nb/V is more than or equal to 2, and Nb/Ti is more than or equal to 1.
On the other hand, the invention provides a preparation method of the high-strength high-corrosion-resistance super austenitic stainless steel, which comprises the following steps:
(1) smelting by adopting an electric furnace/converter, AOD and LF process to obtain stainless steel water with qualified components;
(2) continuously casting or die casting the stainless steel water to obtain a casting blank;
(3) homogenizing the casting blank, and then forging or hot rolling to obtain a steel plate;
(4) and carrying out solution treatment and aging treatment on the steel plate to obtain the high-strength high-corrosion-resistance super austenitic stainless steel.
According to the preparation method of the high-strength high-corrosion-resistance super austenitic stainless steel, the homogenization treatment comprises the steps of heating a casting blank to 1250-1280 ℃, and preserving heat for 24-48 hours.
According to the preparation method of the high-strength high-corrosion-resistance super austenitic stainless steel, before forging or hot rolling, the casting blank is heated to 1200-1240 ℃ and is kept warm for 2-4 hours.
According to the preparation method of the high-strength high-corrosion-resistance super austenitic stainless steel, the forging or hot rolling is carried out at the start forging or start rolling temperature of 1150-1200 ℃, and the finish forging or finish rolling temperature is above 950 ℃.
According to the preparation method of the high-strength high-corrosion-resistance super austenitic stainless steel, the solid solution treatment comprises heat preservation at 1120-1150 ℃ for 30-45 min, and the aging treatment comprises heat preservation at 500 ℃ for 4 h.
In the preparation method of the high-strength high-corrosion-resistance super austenitic stainless steel, the yield strength R of the high-strength high-corrosion-resistance super austenitic stainless steelp0.2More than or equal to 400MPa, tensile strength Rm more than or equal to 750MPa, and elongation after fracture more than or equal to 45 percent; 100 deg.C, 200 deg.C, 300 deg.CYield strength R at 400 ℃ and 500 DEG Cp0.2Is respectively more than or equal to 250MPa, 220MPa, 200MPa, 190MPa and 170 MPa; uniform corrosion rate not more than 0.25 g.m under the condition of 80 ℃ and 60% sulfuric acid-2·h-1The critical pitting temperature is more than 100 ℃, the critical crevice corrosion temperature is more than or equal to 90 ℃, and critical Cl which can cause crevice corrosion in the environment of the simulated desulfurizing tower-The content is more than or equal to 10000ppm and Cl-The stress corrosion cracking critical stress is more than or equal to 100MPa at 200 ℃/500 hours under the environment.
Compared with the prior art, the high-strength high-corrosion-resistance super austenitic stainless steel produced by adopting the components and the preparation process has the following beneficial technical effects:
(1) the high-strength high-corrosion-resistance super austenitic stainless steel has good room-temperature mechanical properties: yield strength Rp0.2More than or equal to 400MPa, tensile strength Rm more than or equal to 750MPa, and elongation after fracture more than or equal to 45 percent;
(2) the high-strength high-corrosion-resistance super austenitic stainless steel has excellent high-temperature yield strength: yield strength R at 100 deg.C, 200 deg.C, 300 deg.C, 400 deg.C, 500 deg.Cp0.2Is respectively more than or equal to 250MPa, 220MPa, 200MPa, 190MPa and 170 MPa;
(3) the high-strength high-corrosion-resistance super austenitic stainless steel has excellent corrosion resistance: uniform corrosion rate (80 deg.C, 60% sulfuric acid) less than or equal to 0.25 g.m-2·h-1Critical Pitting Temperature (CPT) is more than 100 ℃, critical Crevice Corrosion Temperature (CCT) is more than or equal to 90 ℃, and critical Cl which can cause crevice corrosion in simulated desulfurizing tower environment-The content is more than or equal to 10000ppm and Cl-The stress corrosion cracking critical stress is more than or equal to 100MPa at 200 ℃/500 hours under the environment.
Detailed Description
The present invention will be described in detail with reference to the following embodiments in order to fully understand the objects, features and effects of the invention. The process of the present invention employs conventional methods or apparatus in the art, except as described below. The following noun terms have meanings commonly understood by those skilled in the art unless otherwise specified.
The design concept of the high-strength high-corrosion-resistance super austenitic stainless steel comprises the following components: on the basis of referring to the components of the prior mainly used super austenitic stainless steel, the contents of C and N are properly improved, and meanwhile, Nb and V strengthening elements are added, so that a small amount of fine dispersed M (C, N) phases are precipitated in the service process, and the precipitation strengthening effect is achieved; properly increasing the content of Cu element, and separating out a proper amount of epsilon-Cu phase in the service process to play a role in strengthening precipitation; properly reducing the content of Mo, adding W to replace the corrosion resistance of the Mo, and simultaneously adding a small amount of Co to inhibit the phenomena of coarsening and growth of a harmful sigma phase in the service process, improve the stability of the structure, improve the toughness and simultaneously inhibit the occurrence of pitting corrosion; properly improving Cr element to improve corrosion resistance, and simultaneously matching proper Ni, Mn and N to stabilize austenite; the addition of appropriate B, Ce purifies the grain boundary, prevents P, S harmful elements from being segregated in the grain boundary, improves the grain boundary structure, fills the grain boundary vacancy, reduces the high-temperature grain boundary sliding tendency, improves the grain boundary strength and greatly improves the hot workability.
Specifically, the high-strength high-corrosion-resistance super austenitic stainless steel comprises the following components in percentage by weight: 0.01 to 0.03 percent of C, 0.3 to 0.7 percent of Si, 1 to 2.5 percent of Mn, less than or equal to 0.040 percent of P, less than or equal to 0.004 percent of S, 21 to 24 percent of Cr, 17 to 20 percent of Ni, 4.5 to 6 percent of Mo, 0.5 to 2.5 percent of W, 1 to 2.5 percent of Cu, 0.1 to 0.4 percent of Nb, 0.05 to 0.25 percent of V, 0.1 to 0.4 percent of Ti, 0.3 to 0.7 percent of Co, 0.23 to 0.3 percent of N, 0.001 to 0.005 percent of B, 0.005 to 0.03 percent of Ce, and the balance of Fe and other inevitable impurity elements; preferably, the composition comprises the following components in percentage by weight: 0.015 to 0.03 percent of C, 0.4 to 0.7 percent of Si, 1 to 2 percent of Mn, less than or equal to 0.035 percent of P, less than or equal to 0.003 percent of S, 22 to 24 percent of Cr, 17 to 19 percent of Ni, 5 to 6 percent of Mo, 0.5 to 2 percent of W, 1 to 2 percent of Cu, 0.2 to 0.4 percent of Nb, 0.05 to 0.2 percent of V, 0.1 to 0.3 percent of Ti, 0.3 to 0.6 percent of Co, 0.23 to 0.28 percent of N, 0.001 to 0.004 percent of B, 0.005 to 0.02 percent of Ce, and the balance of Fe and other inevitable impurity elements; most preferably, the composition comprises the following components in percentage by weight: 0.02 to 0.03 percent of C, 0.4 to 0.6 percent of Si, 1 to 1.5 percent of Mn, less than or equal to 0.03 percent of P, less than or equal to 0.002 percent of S, 22 to 23 percent of Cr, 18 to 19 percent of Ni, 5 to 5.5 percent of Mo, 1 to 2 percent of W, 1.5 to 2 percent of Cu, 0.2 to 0.3 percent of Nb, 0.1 to 0.2 percent of V, 0.2 to 0.3 percent of Ti, 0.4 to 0.6 percent of Co, 0.25 to 0.28 percent of N, 0.002 to 0.004 percent of B, 0.01 to 0.02 percent of Ce, and the balance of Fe and other inevitable impurity elements.
Further preferably, the high-strength and high-corrosion-resistance super austenitic stainless steel has the advantages that Nb + V + Ti is less than or equal to 1 percent, Nb/V is more than or equal to 2, and Nb/Ti is more than or equal to 1.
The reason for the limitation of the content range of the main alloying elements will be described in detail below.
C is an austenitizing element, and generally in super austenitic stainless steel, C is considered as a harmful element because M23C6 carbide generated by C and Cr is easy to enrich in grain boundaries and is a main forming element for reducing corrosion resistance, but in the invention, in order to improve strength, a small amount of C is required to be added to more than 0.01 percent to form M (C, N) type carbonitride with Nb, Ti and V, so that the corrosion resistance is not reduced while the high-temperature yield strength and creep strength are improved, and after the C content exceeds 0.03 percent, the grain boundaries are easy to form M23C6 carbide to increase the intergranular corrosion cracking tendency. When the carbon content is 0.015-0.03%, the performance is better, and when the carbon content is 0.02-0.03%, the performance is optimal.
Si is added as a deoxidizer for smelting, can reduce weldability after being excessive, and can easily form harmful topologically close-packed phases in the long-term service process at high temperature, thereby influencing the structural stability and causing the performance deterioration. Therefore, the Si content is limited to 0.3% to 0.7%, preferably 0.4% to 0.7%, and most preferably 0.4 to 0.6%.
The main function of Mn in super austenite is to stabilize austenite phase and also to improve the solubility of N element in steel, and because the invention properly improves Cr content and N content, Mn content must be above 1% in order to achieve full austenite structure and match N content. However, when the amount is increased to 2.5% or more, MnS inclusions are easily formed with S, and MnS provides a favorable site for pitting nucleation after dissolution during corrosion, thereby accelerating the occurrence of pitting corrosion and deteriorating the corrosion resistance, which may affect hot workability. The super austenitic stainless steel has better performance when the Mn content is 1-2%, and the super austenitic stainless steel has the best performance when the Mn content is 1-1.5%. S and P are harmful impurity elements, and the performance of steel grades applied in severe corrosive environments is greatly damaged, so that the P is required to be less than or equal to 0.04 percent, and the S is required to be less than or equal to 0.004 percent.
Cr is the most important alloying element forming the passive film of stainless steel. Generally, the super austenitic stainless steel has a double-layer passivation film structure, wherein the main component of an outer passivation film is iron oxide, and the main component of an inner passivation film is chromium oxide. When the chromium content is high, a compact oxide film can be automatically generated on the metal surface to separate the metal matrix from the external corrosion environment and prevent the metal matrix from being corroded. Therefore, the high chromium content can improve the intergranular corrosion resistance of the austenitic stainless steel. In order to achieve the above effects, the Cr content is increased to 21% or more, but if the Cr element content exceeds 24%, the austenite stability is lowered. Preferably, the Cr content is 22% to 24%, most preferably 22% to 23%.
Ni is also the main alloying element of stainless steel passive films. The Ni and the Cr have synergistic effect to improve the density of the inner-layer passive film and reduce the shearing and breakdown speed of the passive film of the austenitic stainless steel in a corrosive environment. The Ni element can enable the austenitic stainless steel to obtain a complete austenite phase component, inhibit the generation of a ferrite phase, have high strength and good plasticity of the complete austenite phase, inhibit the transformation of a martensite phase in a cold machining process, reduce the work hardening tendency and simultaneously improve the thermal stability of the stainless steel, and in order to achieve the effects, the Ni content is increased to be more than 17 percent, and the cost is overhigh when the Ni content exceeds 20 percent. Preferably, the Ni content is limited to 17% to 19%, most preferably 18% to 19%. The super austenitic stainless steel has high Mo element content, can promote the passivation behavior of the stainless steel, thicken a chromium oxide passivation film, accelerate the re-passivation process and improve the pitting corrosion resistance and crevice corrosion resistance. However, the increase of the Mo element promotes precipitation and growth of a harmful σ phase, and degrades the machinability and corrosion resistance of the super austenitic stainless steel. The invention properly reduces the Mo content to 4.5-6%, preferably 5-6%, most preferably 5-5.5% on the basis of 6% Mo stainless steel.
After the Mo content is reduced, in order to compensate for the loss of corrosion resistance, W is added to replace Mo. Studies have shown that 2% W needs to be added for each 1% Mo reduction instead of its effect. Since Mo is reduced by about 1%, the W content is limited to 0.5% to 2.5%, preferably 0.5% to 2%, and most preferably 1% to 2%.
Cu is beneficial to forming an austenitic stainless steel stable phase, but the effect of Cu is far lower than that of nickel, the dissolution of Mo in stainless steel can be accelerated by adding Cu, the purification of Cr in the stainless steel and the enrichment of Cr to a surface film are promoted, and the positive effect of improving the corrosion resistance is achieved. Meanwhile, Cu can improve the plasticity of the super austenitic stainless steel and is beneficial to cold machining deformation. The Cu content in the super austenite is increased to more than 1%, fine and dispersed epsilon-Cu phases can be separated out in the use process of the material at the high temperature of about 500 ℃, and the high-temperature yield strength and creep strength are improved by pinning dislocation. The hot workability is deteriorated due to the excessively high Cu content. Therefore, the maximum Cu content is limited to 2.5%. Preferably, the Cu content is 1% to 2%, most preferably 15% to 2%.
Nb and V can form dispersed M (C, N) phase in steel, so as to improve strength and high-temperature creep property, prevent austenite grains from growing abnormally and improve intergranular corrosion resistance. However, the high content of the three elements can affect the weldability, promote the formation of low-melting eutectic compounds in the hot working process and increase the cracking tendency. Therefore, the contents of the three elements Nb, V and Ti are respectively limited to Nb 0.1-0.4%, V0.05-0.25%, Ti 0.1-0.4%, preferably Nb 0.2-0.4%, V0.05-0.2%, Ti 0.1-0.3%, most preferably Nb 0.2-0.3%, V0.1-0.2% and Ti 0.2-0.3%, meanwhile, in order to ensure the stability of precipitated phases, the total amount and the proportion of the two elements need to be reasonably matched, and the requirements of (Nb + V + Ti)% being less than or equal to 1%, Nb/V being more than or equal to 2 and Nb/Ti being more than or equal to 1 are met.
Co can inhibit the coarsening and growth of sigma phase in the aging process, thereby improving the strength of the material in the long-term service process. However, since Co is expensive, the amount of Co to be added is limited. Therefore, the content of Co in the present invention is 0.3% to 0.7%, preferably 0.3% to 0.6%, and most preferably 0.4 to 0.6%.
N can improve the stability of austenite, inhibit the generation of intermetallic phases and improve the mechanical property and the hot working property of the stainless steel; in addition, the N element is mainly enriched in the lower layer of the chromium oxide passivation film, so that the stability of the passivation film is improved, the corrosion resistance of Cr and Mo in the super austenitic stainless steel can be enhanced, and the passivation performance and the pitting corrosion resistance of the stainless steel are improved. In the invention, N is further increased to more than 0.23%, and the formation of M (C, N) can be ensured. However, N contents exceeding 0.3% cause a decrease in toughness and increase in difficulty in smelting and processing. Preferably, the N content is from 0.23% to 0.28%, most preferably from 0.25% to 0.28%.
B is added as a trace element, and can play a role in purifying grain boundaries so as to improve the strength of the grain boundaries and improve the creep resistance, but when B is excessive, a low-melting-point phase is formed to promote the generation of welding thermal cracks. Therefore, the content of B is limited to 0.001 to 0.005%, preferably 0.001 to 0.004%, and most preferably 0.002 to 0.004%.
Ce is used as a rare earth element, so that P, S harmful elements can be prevented from being segregated in a grain boundary, the grain boundary structure is improved, grain boundary vacancies are filled, the high-temperature grain boundary sliding tendency is reduced, and the grain boundary strength is improved. However, when the content exceeds 0.03%, excessive oxide inclusions are easily formed, and the weldability is deteriorated. Therefore, the Ce content is limited to 0.005% to 0.03%, preferably 0.005% to 0.02%, and most preferably 0.01% to 0.02%.
According to the invention, through reasonably adjusting the components and the content of each component of the austenitic stainless steel, each element exerts a synergistic effect, the room-temperature mechanical property, the high-temperature yield strength and the corrosion resistance of the austenitic stainless steel are greatly improved, and the super austenitic stainless steel with high strength and high corrosion resistance is obtained.
On the other hand, the invention also provides a preparation method of the high-strength high-corrosion-resistance super austenitic stainless steel, which comprises the following steps:
(1) smelting by adopting an electric furnace/converter, AOD and LF process to obtain stainless steel water with qualified components;
(2) continuously casting or die casting the stainless steel water to obtain a casting blank;
(3) homogenizing the casting blank, and then forging or hot rolling to obtain a steel plate;
(4) and carrying out solution treatment and aging treatment on the steel plate to obtain the high-strength high-corrosion-resistance super austenitic stainless steel.
Wherein the stainless steel water with qualified components comprises, by weight, 0.01% -0.03% of C, 0.3% -0.7% of Si, 1% -2.5% of Mn, less than or equal to 0.040% of P, less than or equal to 0.004% of S, 21% -24% of Cr, 17% -20% of Ni, 4.5% -6% of Mo, 0.5% -2.5% of W, 1% -2.5% of Cu, 0.1% -0.4% of Nb, 0.05% -0.25% of V, 0.1% -0.4% of Ti, 0.3% -0.7% of Co, 0.23% -0.3% of N, 0.001% -0.005% of B, 0.005% -0.03% of Ce, and the balance of Fe and other inevitable impurity elements; preferably, the composition comprises the following components in percentage by weight: 0.015 to 0.03 percent of C, 0.4 to 0.7 percent of Si, 1 to 2 percent of Mn, less than or equal to 0.035 percent of P, less than or equal to 0.003 percent of S, 22 to 24 percent of Cr, 17 to 19 percent of Ni, 5 to 6 percent of Mo, 0.5 to 2 percent of W, 1 to 2 percent of Cu, 0.2 to 0.4 percent of Nb, 0.05 to 0.2 percent of V, 0.1 to 0.3 percent of Ti, 0.3 to 0.6 percent of Co, 0.23 to 0.28 percent of N, 0.001 to 0.004 percent of B, 0.005 to 0.02 percent of Ce, and the balance of Fe and other inevitable impurity elements; most preferably, the composition comprises the following components in percentage by weight: 0.02 to 0.03 percent of C, 0.4 to 0.6 percent of Si, 1 to 1.5 percent of Mn, less than or equal to 0.03 percent of P, less than or equal to 0.002 percent of S, 22 to 23 percent of Cr, 18 to 19 percent of Ni, 5 to 5.5 percent of Mo, 1 to 2 percent of W, 1.5 to 2 percent of Cu, 0.2 to 0.3 percent of Nb, 0.1 to 0.2 percent of V, 0.2 to 0.3 percent of Ti, 0.4 to 0.6 percent of Co, 0.25 to 0.28 percent of N, 0.002 to 0.004 percent of B, 0.01 to 0.02 percent of Ce, and the balance of Fe and other inevitable impurity elements. More preferably, Nb + V + Ti is less than or equal to 1%, Nb/V is more than or equal to 2, and Nb/Ti is more than or equal to 1.
Preferably, the homogenization treatment comprises the steps of heating the casting blank to 1250-1280 ℃, and preserving heat for 24-48 hours to eliminate the segregation of Mo and Nb elements.
Preferably, before the forging or hot rolling, the casting blank is heated to 1200-1240 ℃ and is kept warm for 2-4 hours, so that the uniform heating of the casting blank is ensured, harmful precipitated phases are fully dissolved, and good conditions are created for hot working.
Preferably, the forging or hot rolling is carried out at the beginning forging or beginning rolling temperature of 1150-1200 ℃ and the final forging or final rolling temperature of above 950 ℃ so as to ensure that the material is in the optimal thermoplastic temperature range in the hot working process.
Preferably, the solution treatment comprises heat preservation at 1120-1150 ℃ for 30-45 min, and the aging treatment comprises heat preservation at 500 ℃ for 4h, so as to ensure that the material has excellent strength and corrosion resistance.
Proved by practice, the yield strength R of the high-strength high-corrosion-resistance super austenitic stainless steelp0.2More than or equal to 400MPa, tensile strength Rm more than or equal to 750MPa, and elongation after fracture more than or equal to 45 percent; yield strength R at 100 deg.C, 200 deg.C, 300 deg.C, 400 deg.C, 500 deg.Cp0.2Is respectively more than or equal to 250MPa, 220MPa, 200MPa, 190MPa and 170 MPa; uniform corrosion rate not more than 0.25 g.m under the condition of 80 ℃ and 60% sulfuric acid-2·h-1The critical pitting temperature is more than 100 ℃, the critical crevice corrosion temperature is more than or equal to 90 ℃, and critical Cl which can cause crevice corrosion in the environment of the simulated desulfurizing tower-The content is more than or equal to 10000ppm and Cl-The stress corrosion cracking critical stress is more than or equal to 100MPa at 200 ℃/500 hours under the environment.
Examples
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. Experimental procedures without specifying specific conditions in the following examples were carried out according to conventional methods and conditions.
In table 1, the chemical composition and content of S31254 stainless steel are shown in comparative example 1, the chemical composition and content of N08367 stainless steel are shown in comparative example 2, and the chemical composition and content of 904L stainless steel are shown in comparative example 3. The S31254 stainless steel, the N08367 stainless steel and the 904L stainless steel are all smelted by adopting a known preparation method.
The chemical compositions and contents of the high-strength and high-corrosion-resistance super austenitic stainless steels of examples 1 to 9 are shown in table 1, and the preparation method adopted is as follows: smelting by adopting an electric furnace/converter + AOD + LF process, and obtaining a casting blank through continuous casting or die casting; heating the obtained casting blank to 1250-1280 ℃, and preserving heat for 24-48 hours to eliminate segregation of Mo and Nb elements; after polishing the homogenized casting blank, heating to 1200-1240 ℃, preserving heat for 2-4 hours, then forging or hot rolling, controlling the initial forging (rolling) temperature to 1150-1200 ℃, controlling the final forging (rolling) temperature to more than 950 ℃, and cooling in water or air; carrying out solution treatment at 1120-1150 ℃ for 30-45 min, carrying out water cooling, carrying out aging treatment at 500 ℃ for 4h, and carrying out air cooling to obtain the high-strength high-corrosion-resistance super austenitic stainless steel.
In order to verify how the room-temperature mechanical properties, the high-temperature yield strength and the corrosion resistance of the high-strength and high-corrosion-resistance super austenitic stainless steel of the present invention are, a series of tests were performed on the austenitic stainless steels of examples 1 to 9 and comparative examples 1 to 3, wherein the test methods are all performance test methods commonly used in the art, and the present invention does not specifically describe this.
The results of the room temperature mechanical properties and high temperature yield strength property tests of the austenitic stainless steels of examples 1 to 9 and comparative examples 1 to 3 are shown in Table 2.
The results of the corrosion resistance test of the austenitic stainless steels of examples 1 to 9 and comparative examples 1 to 3 are shown in Table 3.
TABLE 2 summary of the results of the mechanical properties and high temperature yield strength tests of the austenitic stainless steels of examples 1-9 and comparative examples 1-3
As can be seen from the results of the mechanical properties and the high-temperature yield strength tests of the stainless steel shown in Table 2, the room-temperature mechanical properties and the high-temperature yield strength of the high-strength and high-corrosion-resistance super austenitic stainless steel of the embodiments 1 to 9 of the invention are obviously higher than those of S31254 stainless steel, N08367 stainless steel and 904L stainless steel.
TABLE 3 results of the corrosion resistance test of austenitic stainless steels of examples 1 to 9 and comparative examples 1 to 3
As can be seen from the results of the corrosion resistance tests of the austenitic stainless steels shown in Table 3, the high-strength and high-corrosion-resistance super austenitic stainless steels of examples 1 to 9 of the present invention have the performances of uniform corrosion resistance, pitting corrosion resistance, crevice corrosion resistance and stress corrosion resistance obviously higher than those of S31254 stainless steel, N08367 stainless steel and 904L stainless steel.
The present invention has been disclosed in the foregoing in terms of preferred embodiments, but it will be understood by those skilled in the art that these embodiments are merely illustrative of the present invention and should not be construed as limiting the scope of the present invention. It should be noted that all changes and substitutions that are equivalent to these embodiments are deemed to be within the scope of the claims of the present invention. Therefore, the protection scope of the present invention should be subject to the scope defined in the claims.
Claims (9)
1. The super austenitic stainless steel with high strength and high corrosion resistance is characterized by comprising the following components in percentage by weight: 0.01-0.03% of C, 0.3-0.7% of Si, 1-2.5% of Mn, less than or equal to 0.040% of P, less than or equal to 0.002% of S, 21-24% of Cr, 17-19% of Ni, 4.5-6% of Mo, 1-2% of W, 1.5-2.0% of Cu, 0.2-0.3% of Nb, 0.1-0.2% of V, 0.2-0.3% of Ti, 0.4-0.6% of Co, 0.25-0.28% of N, 0.002-0.004% of B, 0.005-0.03% of Ce, less than or equal to 1% of Nb + V + Ti, more than or equal to 2 of Nb/V, more than or equal to 1 of Nb/Ti and the balance of Fe and other inevitable impurity elements.
2. The super austenitic stainless steel with high strength and high corrosion resistance according to claim 1, wherein the composition is, by weight percent: 0.015-0.03% of C, 0.4-0.7% of Si, 1-2% of Mn, less than or equal to 0.035% of P, less than or equal to 0.002% of S, 22-24% of Cr, 17-19% of Ni, 5-6% of Mo, 1-2% of W, 1.5-2.0% of Cu, 0.2-0.3% of Nb, 0.1-0.2% of V, 0.2-0.3% of Ti, 0.4-0.6% of Co, 0.25-0.28% of N, 0.002-0.004% of B, 0.005-0.02% of Ce, less than or equal to 1% of Nb + V + Ti, more than or equal to 2 of Nb/V, more than or equal to 1 of Nb/Ti and the balance of Fe and other inevitable impurity elements.
3. The super austenitic stainless steel with high strength and high corrosion resistance according to claim 2, wherein the composition is, in weight percent: 0.02-0.03% of C, 0.4-0.6% of Si, 1-1.5% of Mn, less than or equal to 0.03% of P, less than or equal to 0.002% of S, 22-23% of Cr, 18-19% of Ni, 5-5.5% of Mo, 1-2% of W, 1.5-2% of Cu, 0.2-0.3% of Nb, 0.1-0.2% of V, 0.2-0.3% of Ti, 0.4-0.6% of Co, 0.25-0.28% of N, 0.002-0.004% of B, 0.01-0.02% of Ce, less than or equal to 1% of Nb + V + Ti, more than or equal to 2 of Nb/V, more than or equal to 1 of Nb/Ti and the balance of Fe and other inevitable impurity elements.
4. The method for preparing the high-strength high-corrosion-resistance super austenitic stainless steel of any of claims 1 to 3, characterized by comprising the following steps:
(1) smelting by adopting an electric furnace/converter, AOD and LF process to obtain stainless steel water with qualified components;
(2) continuously casting or die casting the stainless steel water to obtain a casting blank;
(3) homogenizing the casting blank, and then forging or hot rolling to obtain a steel plate;
(4) and carrying out solution treatment and aging treatment on the steel plate to obtain the high-strength high-corrosion-resistance super austenitic stainless steel.
5. The method for preparing the high-strength high-corrosion-resistance super austenitic stainless steel according to claim 4, wherein the homogenizing treatment comprises heating a casting blank to 1250-1280 ℃ and preserving heat for 24-48 hours.
6. The method for preparing a high-strength high-corrosion-resistance super austenitic stainless steel according to claim 4, wherein the cast slab is heated to 1200 to 1240 ℃ and kept warm for 2 to 4 hours before the forging or hot rolling.
7. The method for preparing a high-strength high-corrosion-resistance super austenitic stainless steel according to claim 4, wherein the forging or hot rolling is performed at a start forging or start rolling temperature of 1150-1200 ℃ and a finish forging or finish rolling temperature of 950 ℃ or higher.
8. The method for preparing the high-strength high-corrosion-resistance super austenitic stainless steel according to claim 4, wherein the solution treatment comprises heat preservation at 1120-1150 ℃ for 30-45 min, and the aging treatment comprises heat preservation at 500 ℃ for 4 h.
9. The method for preparing the high-strength high-corrosion-resistance super austenitic stainless steel according to any one of claims 4 to 8, wherein the yield strength R of the high-strength high-corrosion-resistance super austenitic stainless steelp0.2More than or equal to 400MPa, tensile strength Rm more than or equal to 750MPa, and elongation after fracture more than or equal to 45 percent; yield strength R at 100 deg.C, 200 deg.C, 300 deg.C, 400 deg.C, 500 deg.Cp0.2Is respectively more than or equal to 250MPa, 220MPa, 200MPa, 190MPa and 170 MPa; uniform corrosion rate not more than 0.25 g.m under the condition of 80 ℃ and 60% sulfuric acid-2·h-1The critical pitting temperature is more than 100 ℃, the critical crevice corrosion temperature is more than or equal to 90 ℃, and critical Cl which can cause crevice corrosion in the environment of the simulated desulfurizing tower-The content is more than or equal to 10000ppm and Cl-The stress corrosion cracking critical stress is more than or equal to 100MPa at 200 ℃/500 hours under the environment.
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