CN117660849B - Phosphorus-controlled 00Cr21Ni13Mn5N high-nitrogen austenitic stainless steel and production method thereof - Google Patents
Phosphorus-controlled 00Cr21Ni13Mn5N high-nitrogen austenitic stainless steel and production method thereof Download PDFInfo
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
The invention belongs to the technical field of stainless steel materials, and particularly relates to phosphorus-control 00Cr21Ni13Mn5N high-nitrogen austenitic stainless steel and a production method thereof, wherein the phosphorus-control 00Cr21Ni13Mn5N high-nitrogen austenitic stainless steel comprises the following components in percentage by weight: cr is more than or equal to 20% and less than or equal to 22.5%, C is more than or equal to 0.03%, N is more than or equal to 0.20% and less than or equal to 0.40%, ni is more than or equal to 11.5% and less than or equal to 14%, mn is more than or equal to 4.0% and less than or equal to 6.0%, si is more than or equal to 1.0%, P is more than or equal to 0.015%, S is more than or equal to 0.005%, and the balance is Fe and unavoidable impurities. The phosphorus-controlled 00Cr21Ni13Mn5N austenitic stainless steel has low phosphorus content and uniform grain size, and has higher yield.
Description
Technical Field
The invention belongs to the technical field of stainless steel materials, and particularly relates to phosphorus-controlled 00Cr21Ni13Mn5N high-nitrogen austenitic stainless steel and a production method thereof.
Background
In 1963 Frehser and Kubisch, it was found that the yield strength of austenitic steels increases with increasing nitrogen content, but the toughness is not reduced, and a well-known high-nitrogen austenitic stainless steel was developed. The enterprises of one-weight, double-weight, too-weight, great wall special steel and the like research over 20 years in China from the 80 s, the forging process of the high-nitrogen austenitic stainless steel is gradually stable, and a series of high-nitrogen austenitic stainless steels are developed on the basis. At present, the annual import quantity of high-nitrogen austenitic stainless steel in China reaches more than 7 ten thousand tons (the world metal guide information of 6 months in 2015), and the annual demand of providing information according to terminal clients is about 2 ten thousand tons. The developed 00Cr21Ni13Mn5N austenitic high nitrogen stainless steel is a stainless steel having high strength, excellent corrosion resistance and wear resistance. The welding material has excellent welding performance and processing performance, and is widely applied to the fields of chemical industry, petrochemical industry, ocean engineering, shipbuilding, aerospace and the like. The 00Cr21Ni13Mn5N austenitic stainless steel contains higher nitrogen element, can improve the corrosion resistance and the wear resistance, also contains certain nickel, chromium and other elements, and can keep excellent corrosion resistance in high-temperature or low-temperature environments. The 00Cr21Ni13Mn5N is applied to high-capacity ultra-supercritical thermal power units, nuclear power units, aircraft carrier ejectors, submarines and the like with the power of more than 600MW in China.
The 00Cr21Ni13Mn5N ingot blank produced by the prior art has the problems of poor thermoplasticity, easy cracking during forging, coarse grains of forging materials, mixed crystals and the like, so that the quality of the final product is poor, and the wide application of the final product is adversely affected.
Based on this, there is still room for improvement in the prior art.
Disclosure of Invention
In view of the problems in the prior art, the invention provides phosphorus-controlled 00Cr21Ni13Mn5N high-nitrogen austenitic stainless steel and a production method thereof, and solves the problems that a 00Cr21Ni13Mn5N ingot blank has poor thermoplasticity, is easy to crack during forging, has coarse forging material grains, is mixed with crystals and the like. The 00Cr21Ni13Mn5N high-nitrogen steel with low phosphorus content and uniform grain size is produced, the yield of the existing 00Cr21Ni13Mn5N high-nitrogen steel is improved, and the quality of the existing 00Cr21Ni13Mn5N high-nitrogen steel is improved.
Specifically, according to a first aspect of the present invention, there is provided a phosphorus-controlled 00Cr21Ni13Mn5N high nitrogen austenitic stainless steel comprising the following components in weight percentage: cr is more than or equal to 20% and less than or equal to 22.5%, C is more than or equal to 0.03%, N is more than or equal to 0.20% and less than or equal to 0.40%, ni is more than or equal to 11.5% and less than or equal to 14%, mn is more than or equal to 4.0% and less than or equal to 6.0%, si is more than or equal to 1.0%, P is more than or equal to 0.015%, S is more than or equal to 0.005%, and the balance is Fe and unavoidable impurities.
In the embodiment of the invention, the phosphorus-controlled 00Cr21Ni13Mn5N high-nitrogen austenitic stainless steel is characterized by comprising the following components in percentage by weight: cr:21%, C:0.02%, N:0.27%, ni:13.5%, mn:5.3%, si:0.31%, P:0.013%, S:0.0018% and the balance of Fe and unavoidable impurities.
According to a second aspect of the present invention, there is provided a method for producing phosphorus-controlled 00Cr21Ni13Mn5N high nitrogen austenitic stainless steel, comprising the steps of: s10, adding the raw materials into an electric furnace for smelting to obtain molten steel; and S20, injecting molten steel into an AOD decarburization converter, and then carrying out LF refining, continuous casting and electroslag remelting to obtain an electroslag billet, wherein a phosphorus control scheme is formulated for each step to control the phosphorus content of the final product.
In an embodiment of the present invention, in step S10, a first phosphorus control scheme for an electric furnace includes: C-Mn alloy is avoided in the batching process, and the electric furnace adopts low-P high-chromium and carbon crop to prepare carbon; controlling the smelting temperature in the electric furnace to be 1520-1545 ℃, and removing primary slag; after primary slag is scraped off, the temperature is controlled at 1550-1580 ℃.
In an embodiment of the present invention, the first phosphorus control scheme further includes: under the condition of large slag quantity, slag flows and is replaced in the oxygen blowing process; preventing slag-off rephosphorization during tapping, and controlling the content of tapping phosphorus below 0.03%.
In an embodiment of the present invention, in step S20, a second phosphorus control scheme for an AOD decarbonization converter includes: and when the Mn content is regulated, metal Mn is added, so that the adoption of C-Mn alloy is avoided.
In the embodiment of the present invention, in step S20, the third phosphorus control scheme for LF refining includes: after the LF furnace is fed with a proper amount of Al wires and the slag is well converted, the steel slag friends are added in batches for deep deoxidization and desulfurization until the slag becomes white and the sulfur content is less than 0.002 percent.
In an embodiment of the present invention, in step S20, a fourth phosphorus control scheme for continuous casting pouring includes: the casting temperature is 1440-1450 ℃; when the molten steel surface of the crystallizer submerges the lower hole of the submerged nozzle, the mold flux is added, and the mold flux is timely added in a small adding and duty adding mode in the steel drawing process, so that the slag surface is kept from lightening.
In an embodiment of the present invention, in step S20, a fifth phosphorus control scheme for electroslag remelting includes: adopting a grinding mode to clean iron oxide on the surface of the continuous casting blank; adopting argon protection measures; the water inlet and outlet temperature of the crystallizer is strictly controlled, so that the compactness of the electroslag blank structure is ensured.
In an embodiment of the present invention, the method for producing phosphorus-controlled 00Cr21Ni13Mn5N high nitrogen austenitic stainless steel further comprises: s30, heating the electroslag billet to 1190-1210 ℃, and forging to obtain a forging material; and S40, carrying out solid solution treatment on the forging material, wherein the solid solution temperature is 1080+/-10 ℃.
The phosphorus-controlled 00Cr21Ni13Mn5N austenitic stainless steel has low phosphorus content and uniform grain size, and has higher yield.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are necessary for the description of the embodiments or the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention and that other embodiments may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic flow chart of a method for producing phosphorus-controlled 00Cr21Ni13Mn5N austenitic stainless steel according to one embodiment of the present invention;
FIG. 2 is a Gleeble drawing process diagram;
FIG. 3 is a graph of temperature vs. plasticity for 00Cr21Ni13Mn 5N;
FIG. 4 is a graph of temperature versus intensity for 00Cr21Ni13Mn 5N;
FIG. 5 is a temperature-impact power curve of 00Cr21Ni13Mn 5N;
FIG. 6 is a graph of 00Cr21Ni13Mn5N with different P content versus impact energy;
FIG. 7 is a grain size of 9P1 No. 0.003% P content;
FIG. 8 is a grain size of 9P No. 2, 0.015% P content;
FIG. 9 is a grain size of 9P3 No. 0.033% P content;
FIG. 10 is a diagram showing the surface quality of a wrought material of phosphorus-controlled 00Cr21Ni13Mn5N high nitrogen austenitic stainless steel according to the present invention;
FIG. 11 shows the surface quality of a forged material obtained by an uncontrolled phosphorus process in the prior art;
FIG. 12 is a diagram of the grain size of a wrought material of a phosphorus-controlled 00Cr21Ni13Mn5N high nitrogen austenitic stainless steel according to the present invention;
FIG. 13 is a grain size diagram of a forged material obtained by an uncontrolled phosphorus process according to the prior art.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the following embodiments of the present invention will be described in further detail with reference to the accompanying drawings.
It should be noted that, in the embodiments of the present invention, all the expressions "first" and "second" are used to distinguish two entities with the same name but different entities or different parameters, and it is noted that the "first" and "second" are only used for convenience of expression, and should not be construed as limiting the embodiments of the present invention, and the following embodiments are not described one by one.
In the prior art, a great amount of basic research work is carried out on a method for preparing high-nitrogen steel with high nitrogen content and inhibiting pore formation in the solidification process to control the process and the high-nitrogen steel with high nitrogen content obtained based on the method, and the technical proposal carries out the improvement of nitrogen solubility model, kinetics of nitrogen blowing smelting, thermodynamics of pressurized smelting on nitrogen alloying, kinetics, inhibition of solidification bubbles, segregation and the like. However, in actual production, the high nitrogen steel is extremely easy to crack in the forging process, and the high nitrogen steel can have better thermoplasticity at high temperature, so that the cracking tendency is reduced. However, the grains grow sharply above 1150 ℃, so that the initial forging temperature is not higher than 1200 ℃, usually 1150 ℃, and the final forging temperature is not lower than 800 ℃, usually between 850 ℃ and 900 ℃.
The inventor finds that the manufacturing enterprises of the high-nitrogen steel also have the problem that the content of impurity element (P) is higher in the production process, which can cause the problems of poor thermoplasticity of ingot blanks, easy cracking during forging, coarse grains of forging materials, serious mixed crystals and the like. If the problem of high impurity element (P) content is not solved, the problem of high rejection rate in the mass production of high-nitrogen steel can be solved. For example: the control condition of the main alloy components of the 00Cr21Ni13Mn5N electrode rod is good, the main problem is that the P content is high, the average content is 0.02% -0.04%, the control level can meet the requirements of the conventional austenitic stainless steel, but the content of the high-nitrogen austenitic stainless steel needs to be further reduced. In addition, the 00Cr21Ni13Mn5N high nitrogen steel forgings have serious coarse grain and mixed grain problems.
Therefore, the invention provides the phosphorus-controlled 00Cr21Ni13Mn5N high-nitrogen austenitic stainless steel and the production method thereof, which are used for obtaining the 00Cr21Ni13Mn5N high-nitrogen steel with low phosphorus content and uniform grain size, solving the problems of poor thermoplasticity, easy cracking during forging, coarse forging material grains, serious mixed crystals and the like of the 00Cr21Ni13Mn5N ingot blank, and improving the quality of the 00Cr21Ni13Mn5N high-nitrogen steel.
According to a first aspect of the invention, there is provided a phosphorus-controlled 00Cr21Ni13Mn5N high nitrogen austenitic stainless steel comprising the following components in weight percentage: cr is more than or equal to 20% and less than or equal to 22.5%, C is more than or equal to 0.03%, N is more than or equal to 0.20% and less than or equal to 0.40%, ni is more than or equal to 11.5% and less than or equal to 14%, mn is more than or equal to 4.0% and less than or equal to 6.0%, si is more than or equal to 1.0%, P is more than or equal to 0.015%, S is more than or equal to 0.005%, and the balance is Fe and unavoidable impurities. The P content of the phosphorus-controlled 00Cr21Ni13Mn5N high-nitrogen austenitic stainless steel is lower than that of the same type of high-nitrogen austenitic stainless steel in the prior art, so that the product has better grain size and yield. As shown in fig. 10 to 13, the surface quality of the forging material of the phosphorus-controlled 00Cr21Ni13Mn5N high-nitrogen austenitic stainless steel is obviously better than that of the forging material obtained by the non-phosphorus-controlled original process in the prior art, and the crystal grain size of the forging material of the phosphorus-controlled 00Cr21Ni13Mn5N high-nitrogen austenitic stainless steel is more uniform and is obviously better than that of the forging material obtained by the non-phosphorus-controlled original process in the prior art.
In the embodiment of the invention, the phosphorus-controlled 00Cr21Ni13Mn5N high-nitrogen austenitic stainless steel comprises the following components in percentage by weight: cr:21%, C:0.02%, N:0.27%, ni:13.5%, mn:5.3%, si:0.31%, P:0.013%, S:0.0018% and the balance of Fe and unavoidable impurities.
In the embodiment of the invention, the phosphorus-controlled 00Cr21Ni13Mn5N high-nitrogen austenitic stainless steel comprises the following components in percentage by weight: cr:20%, C:0.01%, N:0.20%, ni:11.5%, mn:4.0%, si:0.35%, P:0.012%, S:0.002%, the balance being Fe and unavoidable impurities.
In the embodiment of the invention, the phosphorus-controlled 00Cr21Ni13Mn5N high-nitrogen austenitic stainless steel comprises the following components in percentage by weight: cr:20.49%, C:0.021%, N:0.359%, ni:13.42%, mn:5.42%, si:0.393%, P:0.003%, S:0.0025% Fe and unavoidable impurities in balance.
In the embodiment of the invention, the phosphorus-controlled 00Cr21Ni13Mn5N high-nitrogen austenitic stainless steel comprises the following components in percentage by weight: cr:22.5%, C:0.025%, N:0.40%, ni:14%, mn:6.0%, si:0.4%, P:0.006%, S:0.005%, the balance being Fe and unavoidable impurities.
According to a second aspect of the present invention, there is provided a method for producing phosphorus-controlled 00Cr21Ni13Mn5N high nitrogen austenitic stainless steel as described in the above-described embodiment, as illustrated in fig. 1, comprising the steps of:
S10, adding the raw materials into an electric furnace for smelting to obtain molten steel; and
S20, injecting molten steel into an AOD decarburization converter, then carrying out LF refining, continuous casting pouring and electroslag remelting to obtain an electroslag steel billet,
Wherein a phosphorus control scheme is formulated for each step to control the phosphorus content of the final product.
In an embodiment of the present invention, in step S10, molten steel is melted according to the following elemental weight percentages: cr is more than or equal to 20% and less than or equal to 22.5%, C is more than or equal to 0.03%, N is more than or equal to 0.20% and less than or equal to 0.40%, ni is more than or equal to 11.5% and less than or equal to 14%, mn is more than or equal to 4.0% and less than or equal to 6.0%, si is more than or equal to 1.0%, P is more than or equal to 0.015%, S is more than or equal to 0.005%, and the balance is Fe and unavoidable impurities. The material mixing requirements are as follows: the furnace burden comprises alloy materials and steel materials. Wherein the alloy material comprises electrolytic manganese (which can be replaced by metal manganese), silicomanganese, carbon manganese, ni plate and high chromium; the steel material includes low P scrap steel, this steel or a return material similar to this steel, etc. Preparing raw materials according to the component proportion, adding the raw materials into an electric furnace for smelting, vacuumizing and filling nitrogen for protection, and obtaining molten steel.
In an embodiment of the invention, a first phosphorus control scheme for an electric furnace comprises: C-Mn alloy is avoided in the batching process, and the electric furnace adopts low-P high-chromium and carbon crop to prepare carbon; controlling the smelting temperature in the electric furnace to be 1520-1545 ℃, and removing primary slag; after primary slag is scraped off, the temperature is controlled at 1550-1580 ℃. Under the condition of large slag quantity, slag flows and is replaced in the oxygen blowing process; preventing slag-off rephosphorization during tapping, and controlling the content of tapping phosphorus below 0.03%.
In an embodiment of the present invention, in step S20, a second phosphorus control scheme for an AOD decarbonization converter includes: and when the Mn content is regulated, metal Mn is added, so that the adoption of C-Mn alloy is avoided. In one embodiment, the AOD control gist is: n 2 is blown into the system, and nitrogen is blown in the whole process; the slag basicity was set at 2.4 (about 3000 kg); lime, alloy and the like are added at 1620 ℃ with single addition less than or equal to 1500kg; adding electrolytic Mn (metal Mn) according to Mn content in actual steel, and adding metal Mn after the oxidation period; the tapping temperature is controlled to 1630-1650 ℃, slag removal is more than or equal to 60% and tapping is performed.
In the embodiment of the present invention, in step S20, the third phosphorus control scheme for LF refining includes: after the LF furnace is fed with a proper amount of Al wires and the slag is well converted, the steel slag friends are added in batches for deep deoxidization and desulfurization until the slag becomes white and the sulfur content is less than 0.002 percent. In one embodiment, the LF furnace is fed with a proper amount of Al wires, and after slag formation, steel slag friends are added in batches for deep deoxidization and desulfurization; checking the slag once every predetermined time (e.g., 5 minutes) until the slag becomes white, so that the sulfur content is less than 0.002%; and (5) hoisting ladle tapping at 1450-1460 ℃. The steel slag friends are slag which is similar to the steel slag in composition and can be deoxidized and desulfurized (can be sold directly in the market and is convenient to use) and are used for further deoxidizing and desulfurizing in large-scale treatment, and the steel slag friends are not directly added into molten steel and are added into steel slag covered above the molten steel. The steel slag friends mainly comprise Al 2O3, al, caO and the like, and the steel slag is subjected to deoxidation and desulfurization in a gentle and slow mode through contact with molten steel, so that the deoxidation and desulfurization can be performed on the premise of not increasing the Al content in the molten steel (because the deoxidation and desulfurization are not directly added into the molten steel). Steel slag friends are slag with special functions.
In an embodiment of the present invention, in step S20, a fourth phosphorus control scheme for continuous casting pouring includes: the casting temperature is 1440-1450 ℃; when the molten steel surface of the crystallizer submerges the lower hole of the submerged nozzle, the mold flux is added, and the mold flux is timely added in a small adding and duty adding mode in the steel drawing process, so that the slag surface is kept from lightening.
In an embodiment of the present invention, in step S20, a fifth phosphorus control scheme for electroslag remelting includes: adopting a grinding mode to clean iron oxide on the surface of the continuous casting blank; adopting argon protection measures; the water inlet and outlet temperature of the crystallizer is strictly controlled, so that the compactness of the electroslag blank structure is ensured.
In the embodiment of the invention, as shown in fig. 1, the production method of the phosphorus-controlled 00Cr21Ni13Mn5N high-nitrogen austenitic stainless steel further comprises the following steps:
S30, heating the electroslag billet to 1190-1210 ℃, and forging to obtain a forging material; and
S40, carrying out solid solution treatment on the forging material, wherein the solid solution temperature is 1080+/-10 ℃.
In step S30, the electroslag billet is heated to 1190-1210 ℃ by a high-temperature heat treatment furnace and discharged and is forged by a rapid forging machine.
In step S40, the forged material is subjected to solution treatment in a high-temperature heat treatment furnace at 1080±10 ℃.
According to the production method of the phosphorus-controlled 00Cr21Ni13Mn5N high-nitrogen austenitic stainless steel, disclosed by the invention, the phosphorus content in the 00Cr21Ni13Mn5N high-nitrogen austenitic stainless steel is reduced through a reasonable smelting flow, the problems of poor thermoplasticity, easiness in cracking during forging, coarse forging material grains, serious mixed crystals and the like of an ingot blank are solved, and the toughness of the 00Cr21Ni13Mn5N high-nitrogen austenitic stainless steel is further improved.
The invention is further illustrated by the following specific examples:
Example 1
The target components of the 00Cr21Ni13Mn5N austenitic stainless steel with different P contents are shown in table 1, and 3 kinds of experimental steel with the phosphorus contents of 0.003%, 0.015% and 0.033% are respectively smelted.
The billet is heated to 1200 ℃ by a heating furnace, and is rolled into a hot rolled material by a hot rolling tester. After 1080 ℃ solution treatment is carried out on the hot rolled material, a high-temperature tensile test, an impact test and grain size detection at different temperatures are carried out by taking high-temperature tensile and impact test samples.
Table 1 chemical composition of experimental steels
1.1 High temperature tensile test
And (3) carrying out high-temperature tensile test by using a Gleeble3500 thermal simulation tester, measuring the fracture diameter of the sample, and drawing a high-temperature strength and thermoplasticity trend chart according to test data. The dimension of the sample in the direction is 10mm in the longitudinal direction; the test temperature is 850 ℃, 900 ℃, 950 ℃, 1000 ℃, 1050 ℃ and 1100 ℃ respectively, and the total test temperature is 6 systems; the test was performed using A, B duplex samples. The Gleeble stretching process is shown in FIG. 2.
High-temperature tensile test is carried out by a Gleeble thermal simulation tester, and a 00Cr21Ni13Mn5N temperature-plasticity relation curve can be seen from FIG. 3; FIG. 4 shows a temperature-intensity relationship of 00Cr21Ni13Mn 5N. The result shows that the P content has obvious influence on the high-temperature plasticity of 00Cr21Ni13Mn5N, the high-temperature plasticity is obviously reduced along with the increase of the P content, and the high-temperature plasticity is increased along with the increase of the temperature in a test temperature range; the high-temperature plastic reduction of area with the P content of 0.033 percent is up to about 45 percent, and the reduction of width is obvious compared with 0.015 percent of P and 0.003 percent of P; 0.015% P shows a lower plasticity than 0.003% P, but a smaller reduction in the width; the P content has no obvious influence on the high-temperature strength, and the high-temperature strength is obviously reduced along with the temperature rise under different P contents. Therefore, the P content in 00Cr21Ni13Mn5N has obvious influence on high-temperature plasticity.
1.2 Impact test
V-shaped impact test pieces of 10X 55mm were processed and the impact of different P contents on impact toughness was tested.
FIG. 5 shows a temperature-impact energy relationship curve of 00Cr21Ni13Mn 5N; FIG. 6 shows the relationship between the P content and the impact energy of 00Cr21Ni13Mn 5N. The P content in the 00Cr21Ni13Mn5N steel has a certain influence on the Charpy impact absorption work, but the relative influence is smaller, the main reason is that the Mn content of the 00Cr21Ni13Mn5N steel is relatively smaller, the Mn content is about 5%, the effect of mutual promotion segregation of Mn and P is weaker, in addition, the nickel content of the 00Cr21Ni13Mn5N steel is very high, and 13% of Ni ensures the low-temperature toughness of the material, and meanwhile, the influence of the P content on the impact absorption work is weakened.
1.3 Grain size detection
And processing a metallographic sample, and testing the influence of different P contents on grain size.
As shown in FIGS. 7 to 9, the P content has a certain effect on the grain size of 00Cr21Ni13Mn5N, and the grain size does not change much at 0.015% P or less, and the crystal grains become large and mixed crystals exist as the P content increases.
The small knot:
The P content has obvious influence on the high-temperature plasticity of 00Cr21Ni13Mn5N, and the high-temperature plasticity is obviously reduced along with the increase of the P content; at 0.015% P and below, the effect on high temperature plasticity is relatively small. The P content in the 00Cr21Ni13Mn5N steel has a certain influence on the impact toughness, but the stability of the impact toughness is improved due to the high nickel and low manganese ratio of the steel types, and the relative influence is small. When the P content in the 00Cr21Ni13Mn5 steel is 0.015% P or less, the grain size does not change much, and the grains become larger as the P content increases.
Example 2
According to the steelmaking process flow: the composition of the 00Cr21Ni13Mn5N high-nitrogen austenitic stainless steel is shown in Table 2. Heating the electroslag billet to 1190-1210 ℃ through a heating furnace, discharging, and forging through a rapid forging machine; the forging material is subjected to solution treatment by a high-temperature heat treatment furnace: the solid solution temperature is 1080+/-10 ℃. The key step of phosphorus control is in an electric furnace and an AOD decarburization converter.
The specific steps of the steelmaking process flow are as follows:
table 200Cr21Ni13Mn5N high nitrogen austenitic stainless steel chemical composition
| Steel grade | C | Si | Mn | P | S | Cr | N | Ni | Al |
| 00Cr21Ni13Mn5N | 0.02 | 0.31 | 5.3 | 0.013 | 0.0018 | 21.0 | 0.27 | 13.5 | 0.037 |
(1) The material proportioning requirement is as follows: the furnace burden is formed by alloy materials: electrolytic manganese (which can be replaced by metal manganese), silicomanganese, carbon manganese, ni plate and high chromium; steel and iron material: low P scrap steel, this steel or similar this steel return stock, etc.
(2) Smelting in an electric furnace: the scrap iron, pig iron and ferroalloy are proportioned, then are melted by power transmission, and oxygen blowing fluxing is started after a molten pool is formed in the furnace; when the temperature of the molten pool reaches 1540 ℃, primary slag is scraped off; after primary slag is scraped off, the temperature of a molten pool is controlled at 1550-1580 ℃; slag flowing and slag changing are carried out in the oxygen blowing process; preventing slag-off rephosphorization during tapping, and controlling the content of tapping phosphorus below 0.03%.
An electric furnace phosphorus control scheme is as follows: the preparation process is as far as possible not using C-Mn alloy, the electric furnace is changed to use low P high chromium and carbon for cutting head and preparing carbon, so that the phosphorus content in the raw materials is reduced (the phosphorus content in the ingredients in the stainless steel alloy preparation list is high or low, which can cause larger fluctuation of the phosphorus content, so that the raw materials with low P are needed to be selected for controlling the phosphorus content).
In electric steelmaking, the smelting stage and the reduction stage are mainly divided, and the control of raw material conditions, slag conditions and Cr 2O3 content in the reduction slag in the smelting stage is key. The aim is to achieve the following aims:
1. Adding the raw materials.
2. Slag formation is carried out in advance in the melting period.
The early slagging in the melting period has the following effects:
A. stabilizing the arc and shielding the arc;
B. Covering the molten steel surface to prevent heat loss and reduce molten steel gasification;
C. Absorbing and enriching impurities in the molten steel, thereby purifying the molten steel.
D. the volatilization of elements is reduced, and conditions are created for the reduction period.
In order to meet the requirement of slag formation in advance in the melting period, about 50% of the total consumption of lime is added into a basket along with scrap steel and ferroalloy when the scrap steel is proportioned, and simultaneously the slag is added into an electric furnace, and lime, dolomite, slag with certain alkalinity and good fluidity and enough slag are added in batches in the middle and later period of melting.
3. The reduction period fully reduces the slag.
After the melting period is finished, a certain amount of Cr 2O3 is contained in the slag, if chromium is not reduced, the Cr loss is large, the smelting cost is high, in order to fully reduce Cr in the slag, a carbon-oxygen spray gun is adopted to spray Fe-Si powder and carbon powder into the slag, lime or dolomite is added at any time to ensure the alkalinity and fluidity of the slag, in order to fully reduce Cr in the slag, N 2 or Ar is adopted to enhance the reduction dynamics condition, after the slag is reduced, cr 2O3 in the slag reaches less than 5%, the slag has better fluidity, so that a tapping hole is not blocked during tapping, and slag skimming can be smoothly carried out
4. Oxidation of phosphorus.
Research shows that the oxidation reaction of phosphorus mainly occurs at the steel-slag interface, and the reaction formula is:
2[P ] +5 (FeO) = (P 2O5) +5[ fe ] exothermic reaction (1).
The dephosphorization reaction mainly combines with (CaO) to form stable 3CaO.P 2O5 and 4CaO.P 2O5, and usually mainly includes 4CaO.P 2O5. The reaction formula is as follows:
2[P ] +5 (FeO) +4 (CaO) = (4CaO.P 2O5) +5[ Fe ] exothermic reaction (2).
From the thermodynamic conditions of the dephosphorization reaction, dephosphorization depends on three factors: low temperature, high alkalinity slag, high (FeO) slag.
(3) AOD decarburization converter:
Smelting high quality stainless steel using an AOD converter has two core tasks that must be accomplished: one is decarburization, namely, reducing the carbon content in molten steel to be within the range required by steel grades; and secondly, keeping chromium, namely keeping chromium element in molten steel from being oxidized in a large amount to enter slag, and enabling the content of the chromium element to meet the smelting requirement of the molten steel. It is known that decarburization in a converter is carried out by oxidizing carbon in an oxidizing atmosphere. However, the chromium element may be oxidized at the same time as the carbon in the molten steel is oxidized. Thus, when high-quality stainless steel is smelted by an AOD converter, a pair of unavoidable contradictions occur, namely: if decarburization is required, it is impossible to ensure that chromium in the molten steel is not oxidized; if the chromium content in the molten steel is to be ensured, the decarburization purpose cannot be thoroughly achieved. Firstly, partial chromium element in the stainless steel molten steel is oxidized into Cr 2O3 to enter slag; at this time, if appropriate smelting conditions and atmosphere exist, which are sufficient to make the oxidizing ability of the carbon element in the molten steel stronger than that of the chromium element, cr 2O3 in the slag is unstable, and under which the carbon in the molten steel can take oxygen of Cr 2O3 in the slag to generate CO to escape from the converter, and at the same time, the chromium element in the slag is reduced to the molten steel as a main alloy element of stainless steel. If so, the aim of decarburizing and chromium keeping of the stainless steel smelted by the AOD converter is also realized.
The AOD phosphorus control scheme is to add metal Mn when adjusting Mn content, and to avoid C-Mn alloy (because the C-Mn alloy has larger fluctuation of phosphorus content and less phosphorus content in metal Mn).
The writing method comprises the steps of N 2 gas blowing system and nitrogen blowing in the whole process; the slag basicity was set at 2.4 (about 3000 kg); lime, alloy and the like are added at 1620 ℃ with the single addition amount less than or equal to 1500kg; adding metal according to the Mn content in the actual steel and the end of the oxidation period of electrolytic Mn (metal Mn); and the tapping temperature is controlled to 1630-1650 ℃, slag is removed, and 60% of tapping is performed.
The reference protocol (AOD) is as follows:
1) The target temperature was set to 1630-1650 ℃.
2) N 2/Ar gas blowing system: nitrogen is blown in the whole course.
3) The oxygen blowing system is carried out according to the ultra-low carbon stainless steel, and when the carbon content is less than or equal to 0.005% in the later stage of oxygen blowing and sampling analysis, metal Mn is added in batches, and the Mn content is regulated to about 5.5%.
4) Reducing slag alkalinity to 2.4; the ratio of the deoxidizing agent of the reducing agent is as follows: al=5:5.
5) Reduction operation (double slag method).
6) And switching the smelting mode into a reduction mode, and adding the prepared alloy material and slag material.
7) And the first reduction time is 4min, and after the reduction is finished, the temperature measurement and chemical sample sampling are carried out to fully analyze the components. If the temperature of the molten steel is higher, the content of Mn or N can be regulated by using metal Mn or nitriding metal Mn.
8) Slag skimming is carried out until the current steel liquid level is 1/3 (the slag amount in the furnace is less than or equal to 500 kg), the special selection lime is lengthened to 700 kg/furnace, 80 refining slag is 200kg, al blocks (or ingots) are 80-140 kg/furnace (the aluminum content of the feed LF furnace is controlled to be 0.02-0.03%), and fluorite is proper.
9) And (3) taking chemical samples for full analysis of components (comprising nitrogen and aluminum content) for the second reduction time of 4min, sampling back, and feeding other components except the nitrogen content into internal control, and preparing steel after the components are qualified.
(4) Meaning of LF refining: the LF furnace is used as external refining equipment of the converter, and is used for carrying out refining treatments such as temperature control, alloy fine adjustment, deoxidation, desulfurization and homogenization on molten steel components and temperature on primary steelmaking water of the converter. When the ladle furnace is matched with a continuous casting machine, the LF furnace plays a role in buffering between the converter and the continuous casting machine, and qualified molten steel is timely provided for the continuous casting machine. The alloy trimming treatment of molten steel in the LF furnace station can accurately control the molten steel components, the LF furnace provides alloy trimming conditions for molten steel, and meanwhile, the heating function of the LF furnace can ensure the temperature of molten steel.
LF refining protocol:
1) Feeding aluminum wire to 0.03%.
2) And (3) transmitting power, adding up to 120kg (30-50 kg of each batch) of steel slag friends for deep deoxidation and desulfurization, sampling and full analysis, returning, continuously adding up the steel slag friends according to internal control adjusting components (adding N-Cr in batches) to maintain a reducing atmosphere, and sampling and full analysis.
3) The sample returns, the aluminum content in the steel is 0.02-0.04%, and the content of each element is in an internal control range:
Writing: feeding a proper amount of Al wires into an LF furnace, and adding steel slag friends in batches for deep deoxidization and desulfurization after slag formation; checking the slag every 5 minutes until the slag turns white to ensure that the sulfur content is less than 0.002%; and (5) hoisting ladle tapping at 1450-1460 ℃.
The phosphorus control scheme in the LF smelting process is as follows: ① Feeding a proper amount of Al wires into an LF furnace, and adding steel slag friends in batches for deep deoxidization and desulfurization after slag formation; ② The slag was checked every 5 minutes until it turned white.
(5) The control key points of continuous casting are as follows: continuous casting is a heat transfer process, which is a process to convert liquid steel into solid steel, with a defined composition.
The casting temperature is 1440-1450 ℃; when the molten steel surface of the crystallizer submerges the lower hole of the submerged nozzle, the mold flux is added, the mold flux is timely added in the steel drawing process, and the slag surface is kept from brightening by less addition and duty addition.
(6) Electroslag remelting control key points: the components are determined, mainly clean steelmaking, the steel is melted and solidified again, and nonmetallic inclusions in the steel are removed.
Adopting a grinding mode to clean iron oxide on the surface of the continuous casting blank; adopting argon protection measures; the water inlet and outlet temperature of the crystallizer is strictly controlled, so that the compactness of the electroslag blank structure is ensured.
(7) The electroslag billet is transported to a heating furnace in time, the heating temperature is 1190-1210 ℃, the heating time is 4-6 hours, the billet is forged by a rapid forging machine after being discharged from the furnace, and the final forging temperature is more than or equal to 1000 ℃.
(8) Transferring the forging material to a heat treatment process in time for solution treatment: the solid solution temperature is 1080+/-10 ℃ and the water cooling is carried out.
The yield of the forged material produced by the production method of the phosphorus-controlled 00Cr21Ni13Mn5N high-nitrogen austenitic stainless steel is improved by about 12 percent compared with that of the forged material produced by the prior process without phosphorus control.
The technical features of the above embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the application, which are described in detail and are not to be construed as limiting the scope of the application. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the application, which are all within the scope of the application. Accordingly, the scope of protection of the present application is to be determined by the appended claims.
Claims (7)
1. The production method of the phosphorus-controlled 00Cr21Ni13Mn5N high-nitrogen austenitic stainless steel is characterized by comprising the following steps of:
S10, adding the raw materials into an electric furnace for smelting to obtain molten steel; and
S20, injecting molten steel into an AOD decarburization converter, then carrying out LF refining, continuous casting pouring and electroslag remelting to obtain an electroslag steel billet,
Wherein, a phosphorus control scheme is formulated for each step to control the phosphorus content of the final product, wherein, in step S10, a first phosphorus control scheme for an electric furnace comprises: C-Mn alloy is avoided in the batching process, and the electric furnace adopts low-P high-chromium and carbon crop to prepare carbon; controlling the smelting temperature in the electric furnace to be 1520-1545 ℃, and removing primary slag; after primary slag is scraped off, the temperature is controlled to 1550-1580 ℃, and the step S10 comprises: when the materials are proportioned, lime accounting for 50% of the total consumption of lime is added into a material basket along with scrap steel and ferroalloy, and is added into an electric furnace at the same time, and lime and dolomite are added in batches in the middle and later period of melting to obtain slag with certain alkalinity and good fluidity and enough slag quantity, so that the slag formation in advance in the melting period is satisfied; spraying Fe-Si powder and carbon powder into the slag by using a carbon-oxygen spray gun to reduce Cr in the slag; adding calcium oxide to carry out dephosphorization reaction to form stable 3 CaO.P 2O5 and 4 CaO.P 2O5; in step S20, the second phosphorus control scheme for the AOD decarbonization converter includes: metal Mn is added when Mn content is regulated, C-Mn alloy is avoided, and specific technical rules of the AOD comprise: 1) Setting the target temperature to 1630-1650 ℃; 2) Nitrogen blowing is carried out in the whole process; 3) In the later stage of oxygen blowing, when the carbon content is less than or equal to 0.005 percent by sampling analysis, metal Mn is added in batches, and the Mn content is regulated to about 5.5 percent; 4) The alkalinity of the reducing slag is controlled at 2.4; the ratio of the deoxidizing agent of the reducing agent is as follows: al=5:5; 5) The reduction operation adopts a double slag method; 6) Switching the smelting mode into a reduction mode, and adding the prepared alloy material and slag material; 7) The first reduction time is 4min, after the reduction is finished, the temperature is measured, chemical sample is taken, and if the temperature of the molten steel is higher, the content of Mn or N can be regulated by using metal Mn or nitriding metal Mn; 8) Slag skimming to 1/3 of the current steel liquid level, wherein the slag amount in the furnace is less than or equal to 500kg, lime is added to 700 kg/furnace, refining slag is 200kg, al blocks or ingots are 80-140 kg/furnace, the aluminum content in the LF furnace is controlled to be 0.02-0.03%, and fluorite is proper; 9) Taking chemical samples, fully analyzing components, and preparing tapping after the components are qualified except nitrogen content, wherein the second reduction time is 4 min; the third phosphorus control scheme for LF refining includes: sampling and fully analyzing components, controlling the aluminum content in steel to be 0.02-0.04%, wherein the content of each element meets the requirements, and specifically comprises the following steps: feeding a proper amount of Al wires into an LF furnace, and adding steel slag friends in batches for deep deoxidization and desulfurization after slag formation; checking the slag every 5 minutes until the slag turns white to ensure that the sulfur content is less than 0.002%; and (3) hoisting ladle tapping at the temperature of 1450-1460 ℃.
2. The method of producing a phosphorus-controlled 00Cr21Ni13Mn5N high nitrogen austenitic stainless steel of claim 1, wherein the first phosphorus control scheme further comprises: under the condition of large slag quantity, slag flows and is replaced in the oxygen blowing process; preventing slag-off rephosphorization during tapping, and controlling the content of tapping phosphorus below 0.03%.
3. The method for producing a phosphorus-controlled 00Cr21Ni13Mn5N high nitrogen austenitic stainless steel according to claim 1, wherein in step S20, the fourth phosphorus control scheme for continuous casting pouring comprises: the casting temperature is 1440-1450 ℃; when the molten steel surface of the crystallizer submerges the lower hole of the submerged nozzle, the mold flux is added, and the mold flux is timely added in a small adding and duty adding mode in the steel drawing process, so that the slag surface is kept from lightening.
4. The method for producing a phosphorus-controlled 00Cr21Ni13Mn5N high nitrogen austenitic stainless steel according to claim 1, wherein in step S20, a fifth phosphorus control scheme for electroslag remelting comprises: adopting a grinding mode to clean iron oxide on the surface of the continuous casting blank; adopting argon protection measures; the water inlet and outlet temperature of the crystallizer is strictly controlled, so that the compactness of the electroslag blank structure is ensured.
5. The method for producing phosphorus-controlled 00Cr21Ni13Mn5N high nitrogen austenitic stainless steel according to claim 1, further comprising:
S30, heating the electroslag billet to 1190-1210 ℃, and forging to obtain a forging material; and
S40, carrying out solid solution treatment on the forging material, wherein the solid solution temperature is 1080+/-10 ℃.
6. The method for producing phosphorus-controlled 00Cr21Ni13Mn5N high-nitrogen austenitic stainless steel according to claim 1, wherein the 00Cr21Ni13Mn5N high-nitrogen austenitic stainless steel comprises the following components in percentage by weight: cr is more than or equal to 20% and less than or equal to 22.5%, C is more than or equal to 0.03%, N is more than or equal to 0.20% and less than or equal to 0.40%, ni is more than or equal to 11.5% and less than or equal to 14%, mn is more than or equal to 4.0% and less than or equal to 6.0%, si is more than or equal to 1.0%, P is more than or equal to 0.015%, S is more than or equal to 0.005%, and the balance is Fe and unavoidable impurities.
7. The method for producing a phosphorus-controlled 00Cr21Ni13Mn5N high-nitrogen austenitic stainless steel according to claim 6, wherein the 00Cr21Ni13Mn5N high-nitrogen austenitic stainless steel comprises the following components in percentage by weight: cr:21%, C:0.02%, N:0.27%, ni:13.5%, mn:5.3%, si:0.31%, P:0.013%, S:0.0018% and the balance of Fe and unavoidable impurities.
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