CN111057935B - Preparation method of heat-resistant stainless steel - Google Patents
Preparation method of heat-resistant stainless steel Download PDFInfo
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- CN111057935B CN111057935B CN201911355358.5A CN201911355358A CN111057935B CN 111057935 B CN111057935 B CN 111057935B CN 201911355358 A CN201911355358 A CN 201911355358A CN 111057935 B CN111057935 B CN 111057935B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/04—Making ferrous alloys by melting
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/04—Removing impurities by adding a treating agent
- C21C7/064—Dephosphorising; Desulfurising
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/04—Removing impurities by adding a treating agent
- C21C7/072—Treatment with gases
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/001—Ferrous alloys, e.g. steel alloys containing N
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/34—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of silicon
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/08—Iron or steel
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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
- Y02P10/10—Reduction of greenhouse gas [GHG] emissions
- Y02P10/134—Reduction of greenhouse gas [GHG] emissions by avoiding CO2, e.g. using hydrogen
Abstract
The invention discloses a preparation method of heat-resistant stainless steel, which comprises the following steps: carrying out molten steel smelting, annealing and pickling on raw materials of the heat-resistant stainless steel; the molten steel smelting step comprises the raw material input stage management and control of an EAF electric furnace, wherein the raw material ratio is STS + plain carbon steel + ChCr + pure NI; AOD argon oxygen decarburization refining; a pre-desulfurization molten soup desulfurization process is adopted; the continuous casting process adopts CaO-SiO2Is low melting point steel slag molten steel; si + Al deoxidation technology is adopted; the refining process adopts complete slag skimming operation, the aeration time is 12min, and the standing time is more than 30 min; an air curtain retaining wall is added to the tundish; the annealing and pickling step comprises a neutral salt electrolysis section and a mixed acid pickling section. The heat-resistant stainless steel has the beneficial effects that the heat-resistant stainless steel with excellent heat-resistant fatigue performance, high-temperature strength and oxidation resistance is obtained through reasonable design of the components and determination of the production process, and the heat-resistant stainless steel has better economic and social benefits.
Description
Technical Field
The invention belongs to the technical field of stainless steel smelting, and particularly relates to a preparation method of heat-resistant stainless steel.
Background
In recent years, people have been increasingly concerned about global environmental-friendly problems, and in order to adapt to the international trend of resource conservation and environmental friendliness, higher requirements are put forward on parts of an engine exhaust system: on one hand, the heat efficiency is improved, the exhaust emission is reduced, on the other hand, the self weight of the automobile is lightened, and the running speed is improved. With the increasing environmental stress, in 2001 to 2019, the automobile exhaust emission standard of China gradually rises from the state I to the state VI, the automobile exhaust emission standard becomes more strict, and with the implementation of the state VI standard, the automobile type produced in the later period has higher requirements on the exhaust emission. The hot end of the automobile exhaust pipe comprises an exhaust manifold, a front pipe, a corrugated pipe and a catalytic converter, and the temperature is over 600 ℃, so that the stainless steel for the hot end mainly considers the high-temperature performances of the stainless steel, such as thermal fatigue resistance, high-temperature strength, high-temperature oxidation resistance and the like. Along with the gradual increase of the temperature of an engine, great challenge is provided for the high temperature resistance of hot-end stainless steel, and common heat-resistant steel cannot meet the requirement. For domestic automobile manufacturers, a new material which has excellent thermal fatigue resistance, high-temperature strength and oxidation resistance and relatively low price is urgently needed to be searched for to replace common heat-resistant steel so as to achieve the purposes of economy, environmental protection and durability. The austenitic heat-resistant stainless steel has stronger heat resistance and formability, and is suitable for being used in high-temperature environments of automobile engines and parts which are complex to process. At present, the domestic market is mainly EN1.4828 stainless steel imported from south Africa, the known disclosed technology of the stainless steel is only in a component value range, only Tai steel and Bao steel have a small amount of test production in China, but the surface quality, the production stability and the service life of the product have larger differences from those of the EN1.4828 stainless steel.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a preparation method of heat-resistant stainless steel, which is relatively cheap and has excellent heat-resistant fatigue performance, high-temperature strength and oxidation resistance through reasonable design of components and determination of a production process, replaces common heat-resistant steel and imported EN1.4828 stainless steel, and has better economic and social benefits.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of heat-resistant stainless steel is characterized by comprising the following steps: carrying out molten steel smelting, annealing and pickling on the raw materials of the heat-resistant stainless steel;
the molten steel smelting step comprises the following steps: the EAF electric furnace raw material input stage is controlled, the raw material ratio is STS + plain carbon steel + ChCr + pure NI, and P is ensured to be less than or equal to 0.025%; AOD argon oxygen decarburization refining; a pre-desulfurization molten soup desulfurization process is adopted; the continuous casting process adopts CaO-SiO2Is low melting point steel slag molten steel; si + Al deoxidation technology is adopted; the refining process adopts complete slag skimming operation, the aeration time is 12min, and the standing time is more than 30 min; an air curtain retaining wall is added to the tundish;
the acid washing section in the annealing and acid washing step comprises a neutral salt electrolysis section and a mixed acid washing section, wherein the neutral salt electrolysis section comprises electrolysis of a No. 1 tank → electrolysis of a No. 2 tank → brushing of a No. 1 brush roller group → electrolysis of a No. 3 tank → brushing of a No. 2 brush roller group → brushing of a No. 3 brush roller group; the electrolysis of the electrolysis No. 1 tank, the electrolysis No. 2 tank and the electrolysis No. 3 tank are carried out by adopting Na2SO4 solution, and the process parameters comprise the specific gravity of 1.20 +/-0.05, the pH value of 5.0 +/-1.0, the temperature of 75 +/-5 ℃ and the current of 6000 +/-200A; the technological parameters of the brushing of the 1# brush roller group and the brushing of the 2# brush roller group comprise 84 +/-10A of current, 950 +/-200 rmp of rotating speed and 3mm of load, and the bristles are made of carborundum; the technological parameters of the brushing of the 3# brush roller group comprise 15.3 +/-5A of current, 600 +/-200 rmp of rotating speed and 1.5mm of load, and the brush bristles are made of nylon; the mixed acid pickling section comprises mixed acid 1# pickling → mixed acid 2# pickling → mixed acid 3# pickling → 4# brush roller group scrubbing; the technological parameters of the mixed acid No. 1 pickling, the mixed acid No. 2 pickling and the mixed acid No. 3 pickling comprise: HNO380 +/-10 g/L, HF 15 +/-3 g/L, temperature 55 +/-5 ℃ and metal ion concentration less than or equal to 40 g/L; the technological parameters of the 4# brush roller group brushing comprise 15.3 +/-5A of current, 600 +/-200 rmp of rotating speed and 1.5mm of load, and the brush bristles are made of nylon.
Further, the heat-resistant stainless steel comprises the following raw materials in percentage by mass: c: 0.02 to 0.06%, Si: 1.6-2.0%, Mn: 1.0-1.5%, P: less than or equal to 0.035%, S: less than or equal to 0.001%, Cr: 19.0-20.0%, Ni: 11.0-12.0%, N: less than or equal to 0.06 percent, and the balance of Fe and inevitable impurities.
Further, the heat-resistant stainless steel comprises the following raw materials in percentage by mass: c: 0.04%, Si: 1.9%, Mn: 1.25%, P: less than or equal to 0.03%, S: less than or equal to 0.001%, Cr: 19.2%, Ni: 11.4%, N: 0.05%, the balance being Fe and inevitable impurities; the service temperature of the heat-resistant stainless steel is less than or equal to 1000 ℃.
Compared with the prior art, the invention has the beneficial effects that
1. The invention increases the content of Si and Cr under the condition of low C, has excellent fatigue resistance, high-temperature strength, oxidation resistance and high-temperature corrosion resistance, and has 1000 ℃ maximum application temperature and excellent welding performance and processability. The optimized components are obtained by reasonably proportioning the relations among C, Si, Mn, Cr and N in consideration of favorable characteristics such as processability, Si element heat resistance, high-temperature strength and the like during component design.
2. The stainless steel contains Si with high component, the surface oxide film layer is compact, the existing mixed acid pickling is difficult to remove, the neutral salt current is improved on the basis of the existing process aiming at the characteristic, the surface oxide layer is loosened, meanwhile, the surface is subjected to secondary treatment by using the high-strength brush roll, the hardness of the bristles is reasonably controlled, the brushing effect is ensured, meanwhile, the surface is not damaged, and the pickling quality is ensured.
3. On the basis of the AOD process, the smelting scheme and the brush roll material are reasonably designed, the equipment investment is low, the quality of EN1.4828 materials at the same level can be realized, and the economic maximization effect is realized.
Drawings
The invention will be further explained with reference to the drawings.
FIG. 1 is a graph of heat resistant stainless steel produced according to YS results as a function of temperature with EN 1.4828.
FIG. 2 is a graph showing the temperature dependence of heat-resistant stainless steel produced according to the TS results and EN 1.4828.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
A preparation method of heat-resistant stainless steel is characterized by comprising the following steps: the heat-resistant stainless steel comprises the following raw materials in percentage by mass: c: 0.04%, Si: 1.9%, Mn: 1.25%, P: less than or equal to 0.03%, S: less than or equal to 0.01 percent, Cr: 19.2%, Ni: 11.4%, N: 0.05%, the balance being Fe and inevitable impurities; the service temperature of the heat-resistant stainless steel is less than or equal to 1000 ℃; carrying out molten steel smelting, annealing and pickling on the raw materials of the heat-resistant stainless steel;
the molten steel smelting step comprises the following steps: the EAF electric furnace raw material input stage is controlled, the raw material ratio is STS + plain carbon steel + ChCr + pure NI, and P is ensured to be less than or equal to 0.025%; AOD argon oxygen decarburization refining; a pre-desulfurization molten soup desulfurization process is adopted; the continuous casting process adopts CaO-SiO2Is low melting point steel slag molten steel; si + Al deoxidation technology is adopted; the refining process adopts complete slag skimming operation, the aeration time is 12min, and the standing time is more than 30 min; an air curtain retaining wall is added to the tundish;
the process steps of the invention have the following advantages: 1. in order to ensure the purity, the raw materials of the EAF electric furnace are managed and controlled at the raw material input stage, the raw material ratio is STS + plain carbon steel + ChCr + pure NI, the P is ensured to be less than or equal to 0.025%, the high quality of the raw materials is ensured, and harmful elements and impurities are prevented from being brought in. 2. By adopting the pre-desulfurization molten steel desulfurization technology, the load of AOD loaded S is reduced, the work alkalinity is reduced, Al oxide in molten steel is reduced, and CaO-SiO in continuous casting is reduced2Is low melting point steel slag for preventing Al2O3The method of reducing the aluminum source changes the physical properties of the inclusions; 3. the Si + Al deoxidation technology is adopted, so that the influence of Al on inclusion and welding performance is reduced; 4. and (3) carrying out refining complete slagging-off operation, wherein the aeration time is 12min, and the standing time is more than 30 min. The inclusion analysis is ensured to be fully floated, the air curtain retaining wall is added to the tundish, the inclusion floating removal of the tundish is promoted, and the number of the inclusions is effectively reduced.
The acid washing section in the annealing and acid washing step comprises a neutral salt electrolysis section and a mixed acid washing section, wherein the neutral salt electrolysis section comprises electrolysis of a No. 1 tank → electrolysis of a No. 2 tank → brushing of a No. 1 brush roller group → electrolysis of a No. 3 tank → brushing of a No. 2 brush roller group → brushing of a No. 3 brush roller group; na is adopted for electrolysis in the electrolysis No. 1 tank, electrolysis No. 2 tank and electrolysis No. 3 tank2SO4The solution is operated, and the technological parameters are shown in table 1; the technological parameters of the brushing of the 1# brush roller group, the brushing of the 2# brush roller group, the brushing of the 3# brush roller group and the brushing of the 4# brush roller groupAs shown in table 3; the mixed acid pickling section comprises mixed acid 1# pickling → mixed acid 2# pickling → mixed acid 3# pickling → 4# brush roller group scrubbing; the technological parameters of the mixed acid No. 1 pickling, the mixed acid No. 2 pickling and the mixed acid No. 3 pickling are shown in Table 2.
TABLE 1
TABLE 2
TABLE 3
The heat resistant stainless steel obtained in example 1 was compared with EN1.4828 stainless steel for mechanical properties to give table 4.
TABLE 4
The heat-resistant stainless steel obtained in example 1 and EN1.4828 stainless steel were subjected to Limiting Drawing Ratio (LDR) to obtain Table 5.
TABLE 5
| Sample (I) | LDR |
| Example 1 | 2.12 |
| EN1.4828 | 2.04 |
The heat-resistant stainless steel obtained in example 1 was subjected to an erichson cupping test with EN1.4828 stainless steel to obtain table 6.
TABLE 6
| Erichsenheight(mm) | 1 | 2 | 3 | 4 | 5 | Average |
| Examples | 13.35 | 13.37 | 13.36 | 13.42 | 13.31 | 13.36 |
| EN1.4828 | 13.62 | 13.60 | 13.57 | 13.60 | 13.59 | 13.60 |
The heat-resistant stainless steel obtained in example 1 was subjected to the Hole Expansion Test using EN1.4828 stainless steel, and Table 7 was obtained.
TABLE 7
Mechanical properties of the heat-resistant stainless steel obtained in example 1 and EN1.4828 stainless steel were measured in a Mechanical property test under high temperature environment, YS (MPa) is shown in Table 8 below. TABLE 8
The temperature dependence of heat-resistant stainless steel produced according to the YS (MPa) result and EN1.4828 is shown in FIG. 1.
Mechanical properties of the heat-resistant stainless steel obtained in example were measured in Mechanical properties at high temperature environment using EN1.4828 stainless steel, TS (MPa) and Table 9 was obtained.
TABLE 9
The temperature dependence of the heat-resistant stainless steel produced according to the TS (MPa) results and EN1.4828 is shown in FIG. 2.
The heat-resistant stainless steel obtained in example 1 and EN1.4828 stainless steel were subjected to Oxidation resistance enhanced Temperature Oxidation resistance, and the test contents include: 1. isothermal oxidation at 1000 deg.c for 400 hr (16 days for 16 hr); 2. repeated oxidation at 1100 deg.C for 200 times (27 hr), and heating for 4min → air cooling for 4 min; 3. high temperature salt corrosion, namely, heating for 2 hours → air cooling for 5min → soaking for 5min → atmospheric air for 5min at the temperature of 800 ℃ in 10 cycles (23 hours); the test results shown in Table 10 were obtained.
Watch 10
From the test results, the heat-resistant stainless steel provided by the invention has excellent heat-resistant fatigue performance, high-temperature strength and oxidation resistance through reasonable design of the components and determination of the production process, replaces common heat-resistant steel and imported EN1.4828 stainless steel, and has better economic and social benefits.
Example 2
On the basis of the composition of the raw materials of the heat-resistant stainless steel, the raw materials of the heat-resistant stainless steel can also comprise the following components in percentage by mass: c: 0.02 to 0.06%, Si: 1.6-2.0%, Mn: 1.0-1.5%, P: less than or equal to 0.035%, S: less than or equal to 0.001%, Cr: 19.0-20.0%, Ni: 11.0-12.0%, N: less than or equal to 0.06 percent, and the balance of Fe and inevitable impurities.
It should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and are not limited. Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the scope of the present invention.
Claims (2)
1. A preparation method of heat-resistant stainless steel is characterized by comprising the following steps: the heat-resistant stainless steel comprises the following raw materials in percentage by mass: c: 0.02 to 0.06%, Si: 1.6-2.0%, Mn: 1.0-1.5%, P: less than or equal to 0.035%, S: less than or equal to 0.001%, Cr: 19.0-20.0%, Ni: 11.0-12.0%, N: less than or equal to 0.06 percent, and the balance of Fe and inevitable impurities; carrying out molten steel smelting, annealing and pickling on the raw materials of the heat-resistant stainless steel;
the molten steel smelting step comprises the following steps: the EAF electric furnace raw material input stage is controlled, the raw material proportion is STS + plain carbon steel + ChCr + pure Ni, and the P is ensured to be less than or equal to 0.025%; AOD argon oxygen decarburization refining; a pre-desulfurization molten soup desulfurization process is adopted; the continuous casting process adopts CaO-SiO2Is low melting point steel slag molten steel; si + Al deoxidation technology is adopted; the refining process adopts complete slag skimming operation, the aeration time is 12min, and the standing time is more than 30 min; an air curtain retaining wall is added to the tundish;
the acid washing section in the annealing and acid washing step comprises a neutral salt electrolysis section and a mixed acid washing section, wherein the neutral salt electrolysis section comprises electrolysis of a No. 1 tank → electrolysis of a No. 2 tank → brushing of a No. 1 brush roller group → electrolysis of a No. 3 tank → brushing of a No. 2 brush roller group → brushing of a No. 3 brush roller group; na is adopted for electrolysis in the electrolysis No. 1 tank, electrolysis No. 2 tank and electrolysis No. 3 tank2SO4The solution is operated, the process parameters are that the specific gravity is 1.20 plus or minus 0.05, the pH is 5.0 plus or minus 1.0, the temperature is 75 plus or minus 5 ℃, and the current is 6000 plus or minus 200A; the technological parameters of the brushing of the 1# brush roller group and the brushing of the 2# brush roller group comprise 84 +/-10A of current, 950 +/-200 rpm of rotation speed and 3mm of load, and the brushing materials are carborundum; the technological parameters of the brushing of the 3# brush roller group comprise 15.3 +/-5A of current, 600 +/-200 rpm of rotating speed and 1.5mm of load, and the brush bristles are made of nylon; the mixed acid pickling section comprises mixed acid 1# pickling → mixed acid 2# pickling → mixed acid 3# pickling → 4# brush roller group scrubbing; the technological parameters of the mixed acid No. 1 pickling, the mixed acid No. 2 pickling and the mixed acid No. 3 pickling comprise: HNO380 plus or minus 10g/L, HF 15 plus or minus 3g/L, temperature 55 plus or minus 5 ℃, and metal ion concentration less than or equal to 40 g/L; the technological parameters of the 4# brush roller group brushing comprise 15.3 +/-5A of current, 600 +/-200 rpm of rotating speed and 1.5mm of load, and the brush bristles are made of nylon.
2. A method of manufacturing a heat resistant stainless steel according to claim 1, wherein: the heat-resistant stainless steel comprises the following raw materials in percentage by mass: c: 0.04%, Si: 1.9%, Mn: 1.25%, P: less than or equal to 0.03%, S: less than or equal to 0.01 percent, Cr: 19.2%, Ni: 11.4%, N: 0.05%, the balance being Fe and inevitable impurities; the service temperature of the heat-resistant stainless steel is less than or equal to 1000 ℃.
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