CN113088822A - High-nitrogen, high-strength and low-magnetism austenitic stainless steel middle plate and manufacturing method thereof - Google Patents
High-nitrogen, high-strength and low-magnetism austenitic stainless steel middle plate and manufacturing method thereof Download PDFInfo
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Abstract
The invention provides austenitic stainless steel, which comprises the following components in percentage by weight: less than or equal to 0.03 percent of C, less than or equal to 1.00 percent of Si, 3.00-6.00 percent of Mn, less than or equal to 0.030 percent of P, less than or equal to 0.015 percent of S, 18.00-23.00 percent of Cr, 12.00-18.00 percent of Ni, 2.00-4.00 percent of Mo, 0.20-0.30 percent of N, 0.15-0.25 percent of Nb, and the balance of Fe and inevitable impurities. The invention also provides an austenitic stainless steel plate and a preparation method thereof. The austenitic stainless steel plate has the characteristics of high nitrogen, high strength and low magnetism.
Description
Technical Field
The invention relates to the technical field of special stainless steel products, in particular to a high-nitrogen, high-strength and low-magnetism austenitic stainless steel middle plate and a manufacturing method thereof.
Background
The common austenitic stainless steel represented by 304 has better corrosion resistance and toughness, is widely used in daily production, life and industrial fields, but has lower solid solution state strength (Rp0.2 is generally 260-300 MPa). Cold deformation strengthening is one of the methods for improving the strength of austenite, but because the stability of an austenite structure is poor, the magnetism is easily increased due to deformed martensite after cold deformation, and the application requirements of partial low-magnetism fields cannot be met. Further, the 304 austenitic stainless steel is resistant to Cl because Mo is not contained in the composition-Poor pitting corrosion resistance (Cl resistance)-The pitting index PREN is 18-19, wherein PREN is Cr% +3.3 XMo% + 16N%), and cannot meet the requirement of use in a seawater environment. In view of this, the prior austenitic stainless steel cannot meet the comprehensive requirements of corrosion resistance, high strength and low magnetism provided by partial service environment, so it is very necessary to develop a high-nitrogen, high-strength and low-magnetism austenitic stainless steel.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides high-nitrogen, high-strength and low-magnetism austenitic stainless steel, an austenitic stainless steel plate and a preparation method thereof.
The technical scheme of the invention is as follows:
an austenitic stainless steel comprising, in weight percent: less than or equal to 0.03 percent of C, less than or equal to 1.00 percent of Si, 3.00-6.00 percent of Mn, less than or equal to 0.030 percent of P, less than or equal to 0.015 percent of S, 18.00-23.00 percent of Cr, 12.00-18.00 percent of Ni, 2.00-4.00 percent of Mo, 0.20-0.30 percent of N, 0.15-0.25 percent of Nb, and the balance of Fe and inevitable impurities.
Optionally, the composition comprises, in weight percent: less than or equal to 0.03 percent of C, less than or equal to 1.00 percent of Si, 3.00 to 6.00 percent of Mn, less than or equal to 0.020 percent of P, less than or equal to 0.002 percent of S, 20.50 to 21.50 percent of Cr, 14.00 to 16.00 percent of Ni, 2.00 to 2.50 percent of Mo, 0.20 to 0.30 percent of N, 0.15 to 0.25 percent of Nb, and the balance of Fe and inevitable impurities.
Optionally, Rp0.2 is more than or equal to 400MPa, Rm is more than or equal to 650 MPa.
Optionally, A of the austenitic stainless steel is more than or equal to 35 percent, and Akv is more than or equal to 75J at minus 40 ℃.
Optionally, the relative permeability μ r of the austenitic stainless steel is ≦ 1.01.
Optionally, the pitting corrosion resistance index PREN of the austenitic stainless steel is more than or equal to 31.
An austenitic stainless steel plate is prepared by adopting the austenitic stainless steel.
Optionally, the thickness of the austenitic stainless steel sheet is 8-40 mm.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
the invention utilizes the solid solution strengthening of N, Nb in stainless steel and the austenite stability strengthening of N, Mo makes the surface passive film more compact in stainless steel to improve Cl resistance-The effects of the pitting corrosion performance are synergistic, so that the austenitic stainless steel with high strength, low magnetic conductivity and better corrosion resistance in a solid solution state is obtained, and the service requirement in the marine environment can be met.
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.
Aiming at the problem that the performance of the prior common austenitic stainless steel cannot meet the requirements of partial service environments (such as seawater environments), the inventor of the invention optimizes the elements of the austenitic stainless steel through research, and fully exerts the synergistic effect among the elements, thereby creatively providing the high-nitrogen, high-strength and low-magnetism austenitic stainless steel. The austenitic stainless steel comprises the following components in percentage by weight: less than or equal to 0.03 percent of C, less than or equal to 1.00 percent of Si, 3.00-6.00 percent of Mn, less than or equal to 0.030 percent of P, less than or equal to 0.015 percent of S, 18.00-23.00 percent of Cr, 12.00-18.00 percent of Ni, 2.00-4.00 percent of Mo, 0.20-0.30 percent of N, 0.15-0.25 percent of Nb, and the balance of Fe and inevitable impurities. By the element design, the martensite transformation points Ms and Md (30/50) can be effectively controlled in the machining process, so that the two parameters are kept at the lowest temperature, the martensite is not easy to generate in the cooling and cold machining processes, and the low permeability is finally ensured; meanwhile, the element design can also ensure that the Cr equivalent/Ni equivalent is less than or equal to 1.1, so that the content of delta-ferrite is as low as possible in the process of producing a casting blank; and moreover, the corrosion resistance of the final austenitic stainless steel product can be ensured.
As a preferred embodiment, the austenitic stainless steel of the present invention comprises, in weight percent: less than or equal to 0.03 percent of C, less than or equal to 1.00 percent of Si, 3.00 to 6.00 percent of Mn, less than or equal to 0.020 percent of P, less than or equal to 0.002 percent of S, 20.50 to 21.50 percent of Cr20, 14.00 to 16.00 percent of Ni, 2.00 to 2.50 percent of Mo, 0.20 to 0.30 percent of N, 0.15 to 0.25 percent of Nb0.15, and the balance of Fe and inevitable impurities. Through research, the main performance characteristics of the solid solution state of the plate made of the austenitic stainless steel are shown as follows:
the yield strength Rp0.2 is more than or equal to 400MPa,
the tensile strength Rm is more than or equal to 650MPa,
the elongation A is more than or equal to 35 percent,
the impact energy Akv is more than or equal to 75J at minus 40 ℃,
the relative magnetic permeability mu r is less than or equal to 1.01,
the pitting corrosion resistance index PREN is not less than 31.
The inventor of the invention finds that the low magnetic conductivity is closely related to austenite stabilization design and the content of casting blank delta-ferrite after molten steel solidification through research, and concretely comprises the following steps:
(1) design of austenite stabilization:
as a main basis, the martensite transformation point Ms, Md (30/50) calculation:
ms is 1305-Ni% -41.7 XCR% -33.3 XMn% -27.8 XSi% -1667X (C% + N%), and is the starting temperature for the spontaneous transformation of austenite into martensite in the process of temperature reduction, and is controlled to be less than or equal to-45 ℃ through element design.
Md (30/50) ═ 551-462 × (C% + N%) -9.2 xSi% -8.1 xMn% -13.7 xCr% -29 × (Ni% + C u%) -18.5 xMo% -65 xNb%, Md (30/50) indicates the temperature at which 50% of martensite is generated after 30% cold deformation, and in the present invention, M (30/50) ≦ 330 ℃ is controlled by element design.
The lower the Md (30/50), the less likely it is that induced martensite will be produced during cold-working deformation, ensuring an adverse effect on low permeability during material processing. Wherein the influence of the Ni content on the mutagenized martensitic transformation point is significant, and the martensitic transformation point is lowered with a high Ni content.
(2) Designing the content of casting blank delta-ferrite:
by controlling the Cr equivalent/Ni equivalent to be less than or equal to 1.1', wherein:
cr equivalent% Cr +% Mo +1.5 x% Si +0.5 x% Nb,
ni equivalent% Ni +30 × (% C +% N) +0.5 ×% Mn
In the invention, the content of delta-ferrite can be reduced as much as possible in the process of producing the casting blank by controlling the Cr equivalent/Ni equivalent to be less than or equal to 1.1, thereby ensuring that the finally obtained austenitic stainless steel has high strength and low magnetism.
(3) Designing the pitting corrosion resistance:
the pitting corrosion resistance index PREN ═ Cr% +3.3 × Mo% +16 × N%. According to the invention, PREN is not less than 31 through element design, so that the corrosion resistance of the finally obtained austenitic stainless steel can be ensured.
Based on the design thought, the inventor of the invention provides the austenitic stainless steel, and realizes the synergistic effect among elements by virtue of the selection and the proportion of the elements, wherein the effect of each element is as follows:
c: is an austenite forming element and is beneficial to improving the strength of the stainless steel, but Cr can be precipitated at austenite grain boundaries when the content is too high23C6Causing grain boundary corrosion to occur. Thus, C.ltoreq.0.03% was determined.
Mn: is an austenite forming element, has a solid solution strengthening effect, and is an important element for improving the solubility of N in molten steel together with Cr, but too high is disadvantageous in corrosion resistance. Therefore, the Mn is determined to be between 3.00 and 6.00 percent.
Cr; the Cr content is 20.50-21.50% in order to realize the austenite structure at room temperature.
Ni: is an austenite forming element, is an important element for realizing a pure austenite structure, low magnetic conductivity and high low-temperature impact toughness of the material, and is also a main element for stabilizing austenite, so that the Ni content is determined to be between 14.00 and 16.00 percent.
Mo: is a ferrite forming element, the formed carbide is extremely stable, Mo can make the passive film more compact and firm, thereby effectively improving the marine environment Cl resistance of the stainless steel-The corrosion property is determined to be 2.00-2.50% in consideration of both the balance austenite structure, the low magnetic permeability and the improvement of the corrosion resistance of the material.
N: is a strong austenite forming element, can obviously improve the stability of austenite, improve the strength of steel and resist Cl-The solubility of the above-mentioned alloy is influenced by the contents of Cr and Mn. The content of N is too high, so that the defect of air holes is easily formed in the solidification process of molten steel, and the hot working cracking of the plate is caused, so that the content of N is determined to be 0.20-0.30%.
Nb: is a strong carbide forming element and a ferrite forming element, can play a solid solution strengthening role in austenite solid solution, and can improve the intergranular corrosion resistance of steel and improve the welding performance in the steel. However, the content is too high, so that Nb (C, N) is precipitated at austenite grain boundaries in combination with C, N, and the low-temperature toughness of the material is deteriorated, so that Nb is determined to be between 0.15 and 0.25 percent.
Si: ferrite forming elements are introduced in a proper amount by smelting deoxidation, so that Si is determined to be less than or equal to 1.0 percent.
P: is a harmful element in stainless steel and has adverse effects on the corrosion resistance and low-temperature performance of the stainless steel, so that P is determined to be less than or equal to 0.020%. In the aspect of the smelting process design of stainless steel, the traditional mode of taking scrap steel as a main raw material is changed, and the molten iron for removing P is taken as the main raw material.
S: is a harmful element in stainless steel, aggravates hot working cracking of the stainless steel when the temperature is too high, simultaneously generates MnS inclusions, influences the corrosion resistance of the material, and particularly has more prominent adverse effect on the stainless steel containing high N, high Cr and high Ni, so that the S is determined to be less than or equal to 0.002 percent.
The austenitic stainless steel of the present invention can be made into plates, pipes, etc.
In a preferred embodiment, the invention provides an austenitic stainless steel plate which is prepared by using the austenitic stainless steel, and the thickness of the austenitic stainless steel plate is 8-40 mm.
The preparation method of the austenitic stainless steel plate comprises the steps of preparing a continuous casting billet and processing the continuous casting billet into a medium plate.
The continuous casting billet can be prepared by a conventional method, for example, the following method can be adopted:
AOD (argon oxygen decarburization) process: the de-P molten iron (P is less than or equal to 0.015 percent) replaces argon with nitrogen in the oxidation period and the reduction period, and argon is blown into the molten iron in the reduction period to accurately adjust the nitrogen content. The components of Mo, Ni, Cr and Mn are regulated to the internal control range, especially the [ S ] is less than or equal to 0.003 percent.
An LF procedure: 500-800 kg of lime and 400-700 kg of fluorite are added for slagging in an LF (ladle furnace), ferrocolumbium is added after the LF is electrified for the first time, 30kg of aluminum pills are added into steel after the LF is electrified for slagging, and 300kg of aluminum powder is added into the slag surface. The feeding amount of the silicon-calcium wire is 5.0 m/ton steel; and weak stirring time is 20min after wire feeding.
And (3) continuous casting process: controlling the temperature of the tundish molten steel: 1425 to 1440 ℃. The type of the water gap is an integral water gap, and the insertion depth of the water gap is 140 mm; and (4) putting into an electromagnetic stirrer for stirring.
A coping process: a mode of ' 1.0-1.2% of 16# grinding wheel for two times of coarse grinding and 0.8-1.0% of 20# grinding wheel for one time of fine grinding ' is adopted, the upper surface and the lower surface are required to be uniformly ground, the defects visible to naked eyes are completely ground, and the total grinding loss rate is controlled to be (2.8-3.4)% '.
The thickness of the resulting slab is, for example, 200 mm.
The production of the middle plate comprises a heating process and a heat treatment process.
Wherein the heating process comprises the following steps: the furnace temperature of the heating furnace is 1220 plus or minus 10 ℃, the soaking temperature is 1200 plus or minus 10 ℃, and the total heating time is controlled according to (9-10) min/10mm, namely the heating time is (continuous casting slab thickness/10 mm) × (9-10) min, wherein the unit of the continuous casting slab thickness is millimeter.
Wherein the furnace temperature of the heat treatment process is set to be 1060 +/-10 ℃, the treatment time is 3min/mm, and the steel is taken out of the furnace and quenched by water.
Examples
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
First, the test method of each parameter in the examples is explained as follows:
yield strength Rp, tensile strength Rm, elongation a: implementing GB/T228.1
Akv at-40 ℃: implementing GB/T229
Relative magnetic permeability μ r: performing GB/T35690
The first embodiment is as follows:
the chemical composition of the high-N, high-strength, low-magnetic austenitic stainless steel of the present example is as follows:
c, 0.024% Si, 0.61% Mn, 5.09% P, 0.018% S, 0.001% Cr: 20.92% Ni: 14.57% Mo, 2.44% N, 0.213% Nb, 0.22% balance iron and unavoidable impurities.
Cr equivalent% Cr +% Mo +1.5 ×% Si +0.5 ×% Nb 20.92+2.44+1.5 × 0.61+0.5 × 0.22 ═ 24.38
Ni equivalent% Ni +30 × (% C +% N) +0.5 ×% Mn ═ 14.57+30 × (0.024+0.213) +0.5 × 5.09 ═ 24.225
Cr equivalent/Ni equivalent of 1.006
Pitting resistance index PREN ═ Cr% +3.3 × Mo% +16 × N% + 20.92+3.3 × 2.44+16 × 0.213 ═ 32.38
Ms＝1305-Ni％-41.7×Cr％-33.3×Mn％-27.8×Si％-1667×(C％+N％)
＝1305-14.57-41.7×20.92-33.3×5.09-27.8×0.61-1667×(0.024+0.213)＝-163.5℃
Md(30/50)＝551-462×(C％+N％)-9.2×Si％-8.1×Mn％-13.7×Cr％-29×(Ni％+Cu％)-18.5×Mo％-65×Nb％＝551-462×(0.024+0.213)-9.2×0.61-8.1×5.09-13.7×20.92-29×14.57-18.5×2.44-65×0.22＝-373.9℃
The method for preparing the high-N, high-strength and low-magnetic austenitic stainless steel of the embodiment is as follows:
the de-P molten iron (P is 0.015 percent) is decarbonized and nitrogen-added through an AOD process, components of Mo, Ni, Cr, Mn and the like are adjusted, S is controlled to be 0.003 percent, then 600kg of lime and 500 kg of fluorite are added to an LF station for slagging, ferrocolumbium is added, after electric slagging, 30kg of aluminum pellets are added to steel, and 300kg of aluminum powder is added to the slag surface. The feeding amount of the silicon-calcium wire is 5.0 m/ton steel; and weak stirring time is 20min after wire feeding. Controlling the temperature of the tundish molten steel in the continuous casting process to be 1430-1435 ℃, wherein the water gap is an integral water gap, the insertion depth is 140mm, and the tundish molten steel is electromagnetically stirred; the thickness of the casting blank is 200mm, and the width of the casting blank is 1250 mm; and then, the casting blank is polished, the polishing loss rate is controlled to be 3.0 percent, the two surfaces are required to be uniformly polished, and the defects visible to naked eyes are completely polished.
Heating the polished casting blank by a heating furnace, wherein the temperature of the heating furnace is 1220 +/-10 ℃, the soaking temperature is 1200 +/-10 ℃, and the total heating time is 185 min; the thickness of the middle plate after hot rolling is 40.0 mm; then, the steel is subjected to continuous solution heat treatment, the furnace temperature is 1060 +/-10 ℃, the time is 3min/mm, and the steel is taken out of the furnace and quenched by water.
The properties of the finished plaques are shown in the following table:
| thickness/mm | Rp0.2/MPa | Rm/MPa | A/％ | -40℃Akv/J | Relative magnetic permeability mu r |
| 40.0 | 450 | 770 | 40 | 110 | 1.002 |
Example two:
the high-N, high-strength and low-magnetism austenitic stainless steel comprises the following chemical components:
0.025% Si, 0.56% Mn, 4.94% P, 0.017% S, 0.001% Cr: 20.72% Ni: 14.46% Mo, 2.43% N, 0.28% Nb, 0.18% balance iron and unavoidable impurities.
Cr equivalent% Cr +% Mo +1.5 ×% Si +0.5 ×% Nb 20.72+2.43+1.5 × 0.56+0.5 × 0.18 ═ 24.08
Ni equivalent% Ni +30 × (% C +% N) +0.5 ×% Mn ═ 14.46+30 × (0.025+0.28) +0.5 × 4.94 ═ 26.08
Cr equivalent/Ni equivalent of 0.92
Pitting corrosion resistance index PREN ═ Cr% +3.3 × Mo% +16 × N% + 20.72+3.3 × 2.43+16 × 0.28 ═ 33.22
Ms＝1305-Ni％-41.7×Cr％-33.3×Mn％-27.8×Si％-1667×(C％+N％)
＝1305-14.46-41.7×20.72-33.3×4.94-27.8×0.56-1667×(0.025+0.28)＝-261.9℃
Md(30/50)＝551-462×(C％+N％)-9.2×Si％-8.1×Mn％-13.7×Cr％-29×(Ni％+Cu％)-18.5×Mo％-65×Nb％＝551-462×(0.025+0.28)-9.2×0.56-8.1×4.94-13.7×20.72-29×14.46-18.5×2.43-65×0.18＝-394.9℃
The method for preparing the high-N, high-strength and low-magnetic austenitic stainless steel of the embodiment is as follows:
the de-P molten iron (P is 0.015 percent) is subjected to decarburization and nitrogen increase and component adjustment of Mo, Ni, Cr, Mn and the like through an AOD process, S is controlled to be 0.002 percent, then 600kg of lime and 500 kg of fluorite are added in an LF station for slagging, ferrocolumbium is added, 30kg of aluminum pellets are added in steel after electric slagging, and 300kg of aluminum powder is added on the slag surface. The feeding amount of the silicon-calcium wire is 5.0 m/ton steel; and weak stirring time is 20min after wire feeding. Controlling the temperature of the tundish molten steel in the continuous casting process to be 1430-1440 ℃, wherein the water gap is an integral water gap, the insertion depth is 140mm, and the tundish molten steel is put into an electromagnetic stirrer; the thickness of the casting blank is 200mm, and the width of the casting blank is 1250 mm; and then, the casting blank is polished, the polishing loss rate is controlled to be 3.2 percent, the two surfaces are required to be uniformly polished, and the defects visible to naked eyes are completely polished.
Heating the polished casting blank by a heating furnace, wherein the temperature of the heating furnace is 1220 +/-10 ℃, the soaking temperature is 1200 +/-10 ℃, and the total heating time is 185 min; the thickness of the middle plate after hot rolling is 8.0 mm; then, the steel is subjected to continuous solution heat treatment, the furnace temperature is 1060 +/-10 ℃, the time is 3min/mm, and the steel is taken out of the furnace and quenched by water.
The properties of the finished plaques are shown in the following table:
| thickness/mm | Rp0.2/MPa | Rm/MPa | A/％ | -40℃Akv/J | Relative magnetic permeability mu r |
| 8.0 | 480 | 790 | 42 | 119 | 1.002 |
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other substitutions, modifications, combinations, changes, simplifications, etc., which are made without departing from the spirit and principle of the present invention, should be construed as equivalents and included in the protection scope of the present invention.
Claims (8)
1. An austenitic stainless steel, comprising, in weight percent: less than or equal to 0.03 percent of C, less than or equal to 1.00 percent of Si, 3.00-6.00 percent of Mn, less than or equal to 0.030 percent of P, less than or equal to 0.015 percent of S, 18.00-23.00 percent of Cr, 12.00-18.00 percent of Ni, 2.00-4.00 percent of Mo, 0.20-0.30 percent of N, 0.15-0.25 percent of Nb, and the balance of Fe and inevitable impurities.
2. The austenitic stainless steel of claim 1, comprising, in weight percent: less than or equal to 0.03 percent of C, less than or equal to 1.00 percent of Si, 3.00 to 6.00 percent of Mn, less than or equal to 0.020 percent of P, less than or equal to 0.002 percent of S, 20.50 to 21.50 percent of Cr, 14.00 to 16.00 percent of Ni, 2.00 to 2.50 percent of Mo, 0.20 to 0.30 percent of N, 0.15 to 0.25 percent of Nb, and the balance of Fe and inevitable impurities.
3. Austenitic stainless steel according to claim 1 or 2, characterized in that rp0.2 ≥ 400MPa and Rm ≥ 650 MPa.
4. Austenitic stainless steel according to claim 1 or 2, characterized in that a is 35% or more and Akv 75J is 40 ℃.
5. Austenitic stainless steel according to claim 1 or 2, characterized in that the relative permeability μ r of the austenitic stainless steel is ≤ 1.01.
6. Austenitic stainless steel according to claim 1 or 2, characterized in that the pitting resistance index PREN ≥ 31.
7. An austenitic stainless steel sheet, characterized by being produced by using the austenitic stainless steel according to any one of claims 1 to 6.
8. The austenitic stainless steel sheet according to claim 7, wherein the thickness is 8 to 40 mm.
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