CN111575588A - Martensite precipitation hardening stainless steel and preparation method and application thereof - Google Patents
Martensite precipitation hardening stainless steel and preparation method and application thereof Download PDFInfo
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- C21D2211/008—Martensite
Abstract
The invention discloses a martensite precipitation hardening stainless steel and a preparation method and application thereof, and the martensite precipitation hardening stainless steel comprises the following chemical components: 0.04-0.06% of C; 1.4-1.8% of Si; 0.5-0.9% of Mn0.5; p is less than or equal to 0.035%; s is less than or equal to 0.008 percent; cr 14-14.5%; ni 7-7.8%; al 0-0.15%; mo0.55-0.7%; 0.7-1.0% of Cu0; n0-0.03%; 0.28-0.35% of Ti0.28; the balance of iron and other inevitable impurities; the preparation method comprises the following steps: the raw materials are smelted, continuously cast, hot rolled, thermally annealed and pickled, cold rolled, annealed and pickled, leveled and aged. The method has the advantages that the chemical components of the stainless steel are proportioned, and a smelting process, a hot rolling and rolling process, a cold rolling and rolling process and an annealing process are improved, so that the martensite precipitation hardening stainless steel coil with the yield strength of 1480-1600 MPa is finally obtained.
Description
Technical Field
The invention belongs to the technical field of alloy steel manufacturing, and particularly relates to martensite precipitation hardening stainless steel and a preparation method and application thereof.
Background
High strength stainless steel is widely used in the fields of aviation, aerospace, marine, nuclear industries and the like, and martensite high strength stainless steel is most widely used. Martensitic high strength stainless steel is a stainless steel whose properties can be adjusted by heat treatment. According to the element composition, the martensite high-strength stainless steel is divided into aging stainless steel and precipitation hardening stainless steel. The martensite precipitation hardening stainless steel has the advantages of high strength, good toughness, excellent corrosion resistance and the like after heat treatment. The martensitic precipitation hardening stainless steel commonly used in the market at present is 0Cr17Ni4Cu4Nb, and the common chemical components thereof are as follows by mass percent: carbon (C) is less than or equal to 0.07 percent, manganese (Mn) is less than or equal to 1.00 percent, silicon (Si) is less than or equal to 1.00 percent, phosphorus (P) is less than or equal to 0.023 percent, sulfur (S) is less than or equal to 0.03 percent, chromium (Cr) is 15.50 to 17.50 percent, nickel (Ni) is 3.00 to 5.00 percent, copper (Cu) is 3.00 to 5.00 percent, niobium (Nb) is 0.15 to 0.45 percent, and the balance is iron and other inevitable impurities. 0Cr17Ni4Cu4Nb uses low carbon (C), high chromium (Cr) and copper (Cu), its strength, toughness and corrosion resistance are better than general martensitic stainless steel, it is used in structural member, it depends on Al, Nb and other elements to obtain higher service strength after aging treatment. The coiled material is produced according to the chemical components, and after aging treatment, the strength of about 1000-1400 Mpa can be obtained, which belongs to a low strength grade and can not meet the use requirement of the strength of stainless steel in some environments.
Disclosure of Invention
1. Technical problem to be solved
Aiming at the problems that the strength of 0Cr17Ni4Cu4Nb stainless steel disclosed in the prior art is about 1000-1400 MPa after aging treatment according to the disclosed production coiled material of chemical components, belongs to a low-strength grade and cannot meet the use requirement of the strength of the stainless steel under certain environments, the invention aims to provide the martensite precipitation hardening stainless steel and the preparation method and the application thereof.
2. Technical scheme
In order to achieve the purpose and achieve the technical effect, the invention adopts the following technical scheme:
the martensitic precipitation hardening stainless steel is characterized by comprising the following chemical components in percentage by mass: c: 0.04-0.06%; si: 1.4-1.8%; mn: 0.5-0.9%; p: less than or equal to 0.035%; s: less than or equal to 0.008 percent; cr:14 to 14.5 percent; ni: 7-7.8%; 0 to 0.15 percent of Al; 0.55 to 0.7 percent of Mo; cu: 0.7-1.0%; 0 to 0.03 percent of N; 0.28 to 0.35 percent of Ti; the balance of iron and other inevitable impurities; the preparation steps of the martensitic precipitation hardening stainless steel comprise: smelting and continuously casting each raw material of the martensitic precipitation hardening stainless steel, hot rolling, hot annealing and pickling, cold rolling, annealing and pickling, leveling and aging to obtain the martensitic precipitation hardening stainless steel;
wherein, the hot rolling adopts a secondary hot rolling process; the extraction temperature of a hot rolling heating furnace is 1180-1200 ℃, the furnace time is controlled to be less than 240min, and the plate blank is reheated through hot rolling; firstly, carrying out rough rolling on a casting blank with the thickness of 220mm for 3 times to obtain an initial blank with the thickness of 180-185 mm, carrying out surface confirmation on the initial blank with the thickness of 180-185 mm, and grinding generated cracks; carrying out secondary hot rolling after grinding the primary blank, rolling the primary blank with the thickness of 180-185 mm into a coiled material with the thickness of 4.0-6.0 mm, carrying out 9-pass rolling on the primary blank, namely, carrying out multi-pass low reduction rate, entering the coiled material with the thickness of 23-26 mm before finish rolling, rolling the coiled material into the coiled material with the thickness of 3.5-5.0 mm by 7-pass finish rolling, and carrying out quick cooling by using laminar cooling water during coiling;
the aging is carried out after the flattening, the heating temperature is 500-530 ℃, the heating time is more than or equal to 24Hrs, and the high-strength stainless steel plate with the yield strength of 1480-1600 Mpa can be obtained after the air cooling to the room temperature.
In a specific embodiment of the invention, the smelting and the continuous casting are carried out by an EAF + AOD + VOD + CCP process, VOD adopts a vacuum decarburization technology, vacuum stirring is carried out for 73min, inclusions in steel sufficiently float upwards, and Al deoxidation is used for further reducing Total [ O ] in the steel; in the process of slab Continuous Casting (CCP), the casting speed is preferably not to generate speed fluctuation to cause the liquid level fluctuation of a crystallizer to cause slag entrapment; the most important indexes of the high-strength aging stainless steel, including the content and the form of inclusions have great influence on the toughness of the material.
In a specific embodiment of the invention, the temperature of the steel plate during the thermal annealing and pickling is 1050-1090 ℃, and the production line speed is 10-15 mpm.
In a specific embodiment of the invention, the primary reduction rate of the cold rolling is less than or equal to 40%, and 9-11 passes are adopted in the rolling passes.
In a specific embodiment of the invention, the cold rolling annealing solid solution temperature in the cold rolling annealing pickling is 1020-1070 ℃, when the solid solution temperature is too high, alloy carbides are excessively dissolved into austenite, the stability of the austenite is increased, martensite formation after cooling is reduced, the strength is reduced after precipitation hardening treatment, and the later stage of the product with too high strength is difficult to process when the solid solution temperature is too low, so that the selection of a proper solid solution process has great influence on the later stage precipitation hardening treatment performance.
In a specific embodiment of the invention, the flattening is performed by a leveling device in solution annealing, and the corresponding flatness is achieved according to the application; because the steel grade is a martensite phase transformation steel grade, the martensite phase transformation temperature is actually 80-95 ℃, and the product is easy to generate phase transformation in the production process; because the phase change is uneven, and the precipitated phases are unevenly distributed, the volume change is uneven, residual stress occurs in the tissue, poor flatness is caused, and the required flatness is achieved through flattening.
In a specific embodiment of the present invention, the martensitic precipitation hardening stainless steel comprises the following chemical components by mass percent: c: 0.045%; si: 1.62 percent; mn: 0.72 percent; 0.025 percent of P; 0.0015 percent of S; 14.3 percent of Cr; ni: 7.1 percent; 0.04 to 0.06 percent of Al; 0.65 percent of Mo; cu: 0.82%; 0.01 percent of N; 0.32 percent of Ti; the balance being iron and other unavoidable impurities.
The chemical components and the functions of the high strength martensitic precipitation hardened stainless steel of the present invention will be described in detail below.
Carbon (C), which mainly forms carbides, which are one of the important strengthening phases in steel, the type, composition, amount, size, morphology and distribution of which have a decisive influence on the properties of the steel. Carbides have a high melting point, a high elastic modulus, and high strength and hardness compared to metals, and are brittle substances. The multiple carbides in the steel can be completely solid-dissolved or partially solid-dissolved to form composite carbides. In the present invention, carbon is a main element for forming martensite, and after solid solution cooling, supersaturated carbides are precipitated at grain boundaries to form a low-carbon martensite structure, and primary strengthening is performed. Therefore, in order to ensure good corrosion resistance, weldability and processability, the carbon element content is determined to be 0.04-0.06%, and preferably, the carbon element content is 0.04-0.045%, 0.046-0.050%, 0.051-0.055% and 0.056-0.06%.
Chromium (Cr), which is a main element determining the corrosion resistance of steel, is present in small amounts only to improve the corrosion resistance of steel, but not to make it rust-free. Chromium increases the electrode potential of the solid solution and forms a dense oxide film on the surface. Chromium can effectively improve the pitting potential value of steel and reduce the susceptibility of steel to pitting corrosion, and chromium is an element for strongly forming and stabilizing ferrite and reducing an austenite region. As the content of chromium increases, the tendency of precipitation and formation of some intermetallic compounds increases, and the existence of the intermetallic compounds not only obviously reduces the plasticity and the toughness of the steel, so that the content of chromium element is determined to be 14-14.5%, preferably 14-14.1%, 14.1-14.2%, 14.2-14.3%, 14.3-14.4% and 14.4-14.5%.
Nickel (Ni), which is an indispensable element in martensitic precipitation hardening stainless steel, is also an austenite phase forming element, expands an austenite stable region, and moves toward a high chromium direction as the content of nickel in steel increases, that is, chromium in steel may increase so as not to form a single ferrite structure. In order to ensure that the austenite structure between 815 ℃ and 1100 ℃ is completely transformed into a martensite structure after being cooled to room temperature, the content of nickel in the martensite precipitation hardening stainless steel is 4-20%, but the nickel also reduces the martensite transformation temperature (Ms) point and has stronger action than that of chromium. If the nickel content is too high, the martensite transformation temperature (Ms) point is lowered, and the formation of retained austenite is caused during cooling, so that a full martensite structure cannot be obtained, and the strength after precipitation hardening is lowered. And after precipitation hardening treatment, the nickel element and the titanium element form an intermetallic compound, and secondary strengthening is carried out on the dispersion strengthening phase. In the martensite precipitation hardening stainless steel, the content of nickel element is determined to be 7.0-7.8%, preferably, the content of nickel element is 7.0-7.1%, 7.1-7.2%, 7.2-7.3%, 7.3-7.4%, 7.4-7.5%, 7.5-7.6%, 7.6-7.7%, 7.7-7.8%.
Molybdenum (Mo), an alloying element that is beneficial to strength, toughness, and corrosion resistance in martensitic precipitation hardened stainless steels, is molybdenum. The molybdenum-rich precipitates precipitated at the initial stage of precipitation hardening play an important role in strengthening and maintaining the toughness of the steel. The existence of the alloy element molybdenum in the martensite precipitation hardening steel can also prevent a precipitated phase from being precipitated along the prior austenite grain boundary, thereby avoiding the fracture along the grain and improving the fracture toughness. In certain reducing media, molybdenum can promote the passivation of chromium. Therefore, molybdenum can improve the corrosion resistance of the chromium-nickel stainless steel in sulfuric acid, hydrochloric acid, phosphoric acid and organic acid, effectively inhibit the pitting corrosion tendency of chloride ions and improve the intergranular corrosion resistance of the steel. However, excessive addition of molybdenum also generates retained austenite and lowers the strength after precipitation hardening treatment, as with excessive addition of nickel, so that the content of molybdenum element in the present invention is determined to be 0.55 to 0.7%, preferably 0.55 to 0.58%, 0.58 to 0.61%, 0.61 to 0.64%, 0.64 to 0.67%, 0.67 to 0.7%.
Copper (Cu), a weaker austenite-forming element. The addition of a small amount of copper does not cause significant changes in the structure of the stainless steel. In a corrosive medium, the copper-containing steel forms a copper enrichment layer under an oxidation layer, which can prevent iron oxide from continuously penetrating into the metal, so that the corrosion resistance of the steel in hydrochloric acid and sulfuric acid can be improved by adding copper into the martensite precipitation hardening stainless steel, and the stress corrosion resistance of the steel can also be improved by adding copper. However, since excessive copper content causes copper embrittlement during hot working, the copper content is 0.7 to 1.0%, and preferably, the copper content is 0.7 to 0.74%, 0.74 to 0.78%, 0.78 to 0.82%, 0.82 to 0.86%, 0.86 to 0.90%, 0.90 to 0.95%, 0.95 to 1.0%.
Manganese (Mn), which is an element that expands the γ region, is second only to Ni in steel in its ability to stabilize the austenite structure, and is an element that strongly improves hardenability of steel. Therefore, Mn may partially replace Ni in the martensitic precipitation hardening treated stainless steel. However, the addition of manganese slightly reduces the corrosion resistance of stainless steel with low chromium content, so that the content of manganese element is determined to be 0.5-0.9%, preferably, the content of copper element is 0.5-0.54%, 0.54-0.58%, 0.58-0.62%, 0.62-0.66%, 0.66-0.70%, 0.70-0.74%, 0.74-0.78%, 0.78-0.82%, 0.82-0.86%, 0.86-0.9%.
Titanium (Ti), the most effective alloy strengthening element, increases the titanium content and has more remarkable precipitation strengthening effect, the titanium of the invention is taken as the most main dispersion strengthening element, and after precipitation hardening treatment, a fine dispersion strengthening phase η phase which is Ni is formed in crystal3Ti, which provides sufficient strength to the metal, but increases the content of Ti too much, so that η phase loses its strengthening effect and rather causes severe deterioration of the plasticity and toughness of the steel, therefore, the content of Ti element is determined to be 0.28-0.35%, preferably, the content of Cu element is 0.28-0.29%, 0.29-0.30%, 0.30-0.31%, 0.31-0.32%, 0.32-0.33%, 0.33-0.34%, 0.34-0.35%.
Silicon (Si), which is a strong strengthening ferrite element. Silicon has obvious effect on improving the corrosion resistance of the iron-based and nickel-based corrosion-resistant alloy in a strong oxidation medium. Adding a certain amount of silicon into steel at high temperature or in a strong oxidizing medium to form a silicon-rich surface layer SiO on the surface2Thereby remarkably improving the oxidation resistance or corrosion resistance of the steel. Silicon also has a certain effect on the resistance to sulfuric acid corrosion. The addition of silicon also suppresses the pitting tendency of stainless steel in chloride ion media. Since the content of the silicon element in the present invention is determined to be 1.4 to 1.8% by precipitating the G phase Ni16Ti6Si7 after the precipitation hardening treatment, the content of the silicon element is preferably 1.4 to 1.45%, 1.45 to 1.50%, 1.50 to 1.55%, 1.55 to 1.60%, 1.60 to 1.65%, 1.65 to 1.70%, 1.70 to 1.75%, 1.75 to 1.8%.
Aluminum (Al) is usually added into steel as a deoxidizer, is ferrite forming element, promotes ferrite forming capability to be about 2.5-3 times of that of chromium, and has a main function of precipitation hardening treatment strengthening effect in martensite precipitation hardening treated stainless steel, wherein the content of the aluminum element is determined to be 0-0.15%, and preferably, the content of the aluminum element is 0-0.03%, 0.03-0.06%, 0.06-0.09%, 0.09-0.12%, 0.12-0.15%.
The martensite precipitation hardening stainless steel of the present invention has the alloy components described in the specification, wherein the elements for precipitation hardening strengthening are aluminum (Al), copper (Cu), titanium (Ti) and silicon (Si), thereby obtaining a new high-strength martensite precipitation hardening stainless steel after the precipitation hardening treatment, and the intermetallic compound of Ti, Si and Al is uniformly precipitated in the crystal to strengthen the martensite precipitation hardening stainless steel after the aging treatment, and η phase (Ni) is generated after the precipitation hardening treatment by taking the strengthening element Ti as an example3Ti) and the precipitation strengthening effect is more obvious, so that the high-strength use requirement can be met.
The invention also aims to provide a preparation method of the martensitic precipitation hardening stainless steel, which is characterized in that the martensitic precipitation hardening stainless steel is obtained by smelting and continuously casting, hot rolling, hot annealing and pickling, cold rolling, annealing and pickling, flattening and aging of all raw materials of the martensitic precipitation hardening stainless steel; specifically, the method comprises the following steps:
A. smelting and continuous casting: through EAF + AOD + VOD + CCP, VOD adopts vacuum decarburization technology, vacuum stirring is carried out for 73min, inclusions in steel fully float upwards, inclusions in steel are effectively reduced, and Total [ O ] in steel is further reduced by Al deoxidation, so that the formation of non-metallic oxide inclusions is reduced; in the process of slab Continuous Casting (CCP), the casting speed is preferably not to generate speed fluctuation to cause the liquid level fluctuation of a crystallizer to cause slag entrapment; the most important indexes of the high-strength aging stainless steel, including the content and the form of inclusions have great influence on the toughness of the material;
B. hot rolling: the martensite precipitation hardening stainless steel is sensitive to cracks, and therefore, a secondary hot rolling process is adopted in the design of a rolling process for hot rolling; the extraction temperature of a hot rolling heating furnace is 1180-1200 ℃, the furnace time is controlled to be less than 240min, and the plate blank is reheated through hot rolling; firstly, carrying out rough rolling on a casting blank with the thickness of 220mm for 3 times to obtain an initial blank with the thickness of 180-185 mm, carrying out surface confirmation on the initial blank with the thickness of 180-185 mm, and grinding generated cracks; carrying out secondary hot rolling after grinding the primary blank, rolling the primary blank with the thickness of 180-185 mm into a coiled material with the thickness of 4.0-6.0 mm, in order to ensure that no cracks occur on the surface of a steel plate, carrying out 9-pass rolling on the primary blank, namely carrying out multi-pass low reduction rate, rolling the primary blank into the coiled material with the thickness of 23-26 mm before finish rolling, rolling the coiled material with the thickness of 3.5-5.0 mm by 7-pass rolling, and carrying out rapid cooling by using laminar cooling water during coiling, wherein the supercooled austenite of the steel type is continuously cooled to have a transformation curve, and the martensite transformation temperature (Ms) during rapid cooling is low, so that the martensite produced by phase transformation during cooling is less, and the plate shape;
C. annealing and pickling: the steel plate temperature is 1050-1090 ℃ during thermal annealing and pickling, and the production line speed is 10-15 mpm;
D. cold rolling: the primary reduction rate is less than or equal to 40%, and 9-11 passes are adopted in the rolling pass;
E. cold rolling, annealing and pickling: the cold rolling and annealing solid solution temperature is 1020-1070 ℃, when the solid solution temperature is too high, alloy carbides are excessively dissolved into austenite, the stability of the austenite is increased, the martensite formation after cooling is reduced, the strength is reduced after precipitation hardening treatment, and the later stage of the product with too high strength is difficult to process when the solid solution temperature is too low, so that the later stage precipitation hardening treatment performance is greatly influenced by selecting a proper solid solution process;
F. leveling, wherein the steel grade is a martensite phase transformation steel grade, the martensite phase transformation temperature is actually 80-95 ℃, and the product is easy to generate phase transformation in the production process; due to uneven phase change and uneven distribution of precipitated phases, volume change is uneven, residual stress occurs in the tissue, and poor flatness is caused; therefore, the product after the solution treatment is leveled by leveling equipment, and the corresponding flatness is achieved according to the application;
G. and (3) aging, wherein the flat steel plate is aged at the heating temperature of 500-530 ℃, the heating time is more than or equal to 24Hrs, and the high-strength stainless steel plate with the yield strength of 1480-1600 Mpa can be obtained after air cooling to the room temperature.
The invention also aims to provide application of the martensite precipitation hardening stainless steel in steel belt transmission equipment and die pressing equipment.
3. Advantageous effects
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, through reasonable component design, elements of titanium (Ti), silicon (Si) and aluminum (Al) are added, and during precipitation hardening treatment, a hardening phase is uniformly precipitated for strengthening to obtain required strength and hardness, the preparation process is optimized in the production process, inclusions in steel are reduced, the surface crack defect is improved, certain strength is obtained, and meanwhile, the purity of the steel is improved.
The invention adopts the processes of electric furnace (EAF), external refining (AOD), vacuum stirring (VOD) and deoxidation by adopting aluminum element, so that the oxygen content in steel is reduced to be below 20ppm, and when the oxygen content in steel is extremely low, the generation of inclusions in the steel can be reduced; the preparation process of steel making is improved, nodulation in the casting process is avoided, the total oxygen content in molten steel is reduced, and the purity of the molten steel is improved; hot rolling parameters are optimized, the material plate shape is improved, a novel high-strength stainless steel cold rolling and rolling program is formulated, the occurrence degree of medium waves is reduced as much as possible, and annealing parameters of the high-strength stainless steel are obtained through simulated annealing, so that the high-strength stainless steel has certain performance and good plate shape and meets the surface requirements of higher purposes (inclusion requirements); the size and dispersion degree of a precipitated phase are changed through adjustment of an aging treatment process, the yield strength after simulated aging is 1480-1540 MPa, the hardness HRC 49-51 is realized, and the martensitic precipitation hardening stainless steel with the strength of 1480-1600 MPa can be obtained after aging in actual production.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a graph of yield strength and hardness after a precipitation hardening simulated aging treatment in accordance with the present invention.
FIG. 2 is a structural view of a metallographic structure of a steel grade according to the present invention after precipitation hardening treatment.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The embodiment provides a martensitic precipitation hardening stainless steel, which comprises the following chemical components in percentage by mass: c: 0.045%; si: 1.62 percent; mn: 0.72 percent; 0.025 percent of P; 0.0015 percent of S; 14.3 percent of Cr; ni: 7.1 percent; 0.04 to 0.06 percent of Al; 0.65 percent of Mo; cu: 0.82%; 0.01 percent of N; 0.32 percent of Ti; the balance being iron and other unavoidable impurities. Smelting and continuously casting each raw material of the martensitic precipitation hardening stainless steel, hot rolling, hot annealing and pickling, cold rolling, annealing and pickling, flattening and aging to obtain the martensitic precipitation hardening stainless steel; specifically, the method comprises the following steps:
A. smelting and continuous casting: through EAF + AOD + VOD + CCP, VOD adopts vacuum decarburization technology, vacuum stirring is carried out for 73min, inclusions in steel fully float upwards, inclusions in steel are effectively reduced, and Total [ O ] in steel is further reduced by Al deoxidation, so that the formation of non-metallic oxide inclusions is reduced; in the process of slab Continuous Casting (CCP), the casting speed is preferably not to generate speed fluctuation to cause the liquid level fluctuation of a crystallizer to cause slag entrapment; the most important indexes of the high-strength aging stainless steel, including the content and the form of inclusions have great influence on the toughness of the material;
B. hot rolling: the martensite precipitation hardening stainless steel is sensitive to cracks, and therefore, a secondary hot rolling process is adopted in the design of a rolling process for hot rolling; the extraction temperature of a hot rolling heating furnace is 1180-1200 ℃, the furnace time is controlled to be less than 240min, and the plate blank is reheated through hot rolling; firstly, carrying out rough rolling on a casting blank with the thickness of 220mm for 3 times to obtain an initial blank with the thickness of 180-185 mm, carrying out surface confirmation on the initial blank with the thickness of 180-185 mm, and grinding generated cracks; carrying out secondary hot rolling after grinding the primary blank, rolling the primary blank with the thickness of 180-185 mm into a coiled material with the thickness of 4.0-6.0 mm, in order to ensure that no cracks occur on the surface of a steel plate, carrying out 9-pass rolling on the primary blank, namely carrying out multi-pass low reduction rate, rolling the primary blank into the coiled material with the thickness of 23-26 mm before finish rolling, rolling the coiled material with the thickness of 3.5-5.0 mm by 7-pass rolling, and carrying out rapid cooling by using laminar cooling water during coiling, wherein the supercooled austenite of the steel type is continuously cooled to have a transformation curve, and the martensite transformation temperature (Ms) during rapid cooling is low, so that the martensite produced by phase transformation during cooling is less, and the plate shape;
C. annealing and pickling: the steel plate temperature is 1050-1090 ℃ during thermal annealing and pickling, and the production line speed is 10-15 mpm;
D. cold rolling: the primary reduction rate is less than or equal to 40%, and 9-11 passes are adopted in the rolling pass;
E. cold rolling, annealing and pickling: the cold rolling and annealing solid solution temperature is 1020-1070 ℃, when the solid solution temperature is too high, alloy carbides are excessively dissolved into austenite, the stability of the austenite is increased, the martensite formation after cooling is reduced, the strength is reduced after precipitation hardening treatment, and the later stage of the product with too high strength is difficult to process when the solid solution temperature is too low, so that the later stage precipitation hardening treatment performance is greatly influenced by selecting a proper solid solution process;
F. leveling, wherein the steel grade is a martensite phase transformation steel grade, the martensite phase transformation temperature is actually 80-95 ℃, and the product is easy to generate phase transformation in the production process; due to uneven phase change and uneven distribution of precipitated phases, volume change is uneven, residual stress occurs in the tissue, and poor flatness is caused; therefore, the product after the solution treatment is leveled by leveling equipment, and the corresponding flatness is achieved according to the application;
G. and (3) aging, wherein the flat steel plate is aged at the heating temperature of 500-530 ℃, the heating time is more than or equal to 24Hrs, and the high-strength stainless steel plate with the yield strength of 1480-1600 Mpa can be obtained after air cooling to the room temperature.
Example 2
The embodiment provides a martensitic precipitation hardening stainless steel, which comprises the following chemical components in percentage by mass: c: 0.043 percent; si: 1.74 percent; mn: 0.77 percent; 0.0235 percent of P; 0.0020 percent of S; 14.5 percent of Cr; ni: 7.17 percent; 0.111 percent of Al; 0.75 percent of Mo; cu: 0.86 percent; 0.01 percent of N; 0.225 percent of Ti; the balance being iron and other unavoidable impurities. Smelting and continuously casting each raw material of the martensitic precipitation hardening stainless steel, hot rolling, hot annealing and pickling, cold rolling, annealing and pickling, flattening and aging to obtain the martensitic precipitation hardening stainless steel; specifically, the method comprises the following steps:
A. smelting and continuous casting: through EAF + AOD + VOD + CCP, VOD adopts vacuum decarburization technology, vacuum stirring is carried out for 73min, inclusions in steel fully float upwards, inclusions in steel are effectively reduced, and Total [ O ] in steel is further reduced by Al deoxidation, so that the formation of non-metallic oxide inclusions is reduced; in the process of slab Continuous Casting (CCP), the casting speed is preferably not to generate speed fluctuation to cause the liquid level fluctuation of a crystallizer to cause slag entrapment; the most important indexes of the high-strength aging stainless steel, including the content and the form of inclusions have great influence on the toughness of the material;
B. hot rolling: the martensite precipitation hardening stainless steel is sensitive to cracks, and therefore, a secondary hot rolling process is adopted in the design of a rolling process for hot rolling; the extraction temperature of a hot rolling heating furnace is 1180-1200 ℃, the furnace time is controlled to be less than 240min, and the plate blank is reheated through hot rolling; firstly, carrying out rough rolling on a casting blank with the thickness of 220mm for 3 times to obtain an initial blank with the thickness of 180-185 mm, carrying out surface confirmation on the initial blank with the thickness of 180-185 mm, and grinding generated cracks; carrying out secondary hot rolling after grinding the primary blank, rolling the primary blank with the thickness of 180-185 mm into a coiled material with the thickness of 4.0-6.0 mm, in order to ensure that no cracks occur on the surface of a steel plate, carrying out 9-pass rolling on the primary blank, namely carrying out multi-pass low reduction rate, rolling the primary blank into the coiled material with the thickness of 23-26 mm before finish rolling, rolling the coiled material with the thickness of 3.5-5.0 mm by 7-pass rolling, and carrying out rapid cooling by using laminar cooling water during coiling, wherein the supercooled austenite of the steel type is continuously cooled to have a transformation curve, and the martensite transformation temperature (Ms) during rapid cooling is low, so that the martensite produced by phase transformation during cooling is less, and the plate shape;
C. annealing and pickling: the steel plate temperature is 1050-1090 ℃ during thermal annealing and pickling, and the production line speed is 10-15 mpm;
D. cold rolling: the primary reduction rate is less than or equal to 40%, and 9-11 passes are adopted in the rolling pass;
E. cold rolling, annealing and pickling: the cold rolling and annealing solid solution temperature is 1020-1070 ℃, when the solid solution temperature is too high, alloy carbides are excessively dissolved into austenite, the stability of the austenite is increased, the martensite formation after cooling is reduced, the strength is reduced after precipitation hardening treatment, and the later stage of the product with too high strength is difficult to process when the solid solution temperature is too low, so that the later stage precipitation hardening treatment performance is greatly influenced by selecting a proper solid solution process;
F. leveling, wherein the steel grade is a martensite phase transformation steel grade, the martensite phase transformation temperature is actually 80-95 ℃, and the product is easy to generate phase transformation in the production process; due to uneven phase change and uneven distribution of precipitated phases, volume change is uneven, residual stress occurs in the tissue, and poor flatness is caused; therefore, the product after the solution treatment is leveled by leveling equipment, and the corresponding flatness is achieved according to the application;
G. and (3) aging, wherein the flat steel plate is aged at the heating temperature of 500-530 ℃, the heating time is more than or equal to 24Hrs, and the high-strength stainless steel plate with the yield strength of 1480-1600 Mpa can be obtained after air cooling to the room temperature.
Example 3
The embodiment provides a martensitic precipitation hardening stainless steel, which comprises the following chemical components in percentage by mass: c: 0.0557 percent; si: 1.713%; mn: 0.7 percent; 0.025 percent of P; 0.0016 percent of S; 14.4 percent of Cr; ni: 7.14 percent; 0.045% of Al; 0.62 percent of Mo; cu: 0.77 percent; 0.0068 percent of N; 0.34 percent of Ti; the balance being iron and other unavoidable impurities. Smelting and continuously casting each raw material of the martensitic precipitation hardening stainless steel, hot rolling, hot annealing and pickling, cold rolling, annealing and pickling, flattening and aging to obtain the martensitic precipitation hardening stainless steel; specifically, the method comprises the following steps:
A. smelting and continuous casting: through EAF + AOD + VOD + CCP, VOD adopts vacuum decarburization technology, vacuum stirring is carried out for 73min, inclusions in steel fully float upwards, inclusions in steel are effectively reduced, and Total [ O ] in steel is further reduced by Al deoxidation, so that the formation of non-metallic oxide inclusions is reduced; in the process of slab Continuous Casting (CCP), the casting speed is preferably not to generate speed fluctuation to cause the liquid level fluctuation of a crystallizer to cause slag entrapment; the most important indexes of the high-strength aging stainless steel, including the content and the form of inclusions have great influence on the toughness of the material;
B. hot rolling: the martensite precipitation hardening stainless steel is sensitive to cracks, and therefore, a secondary hot rolling process is adopted in the design of a rolling process for hot rolling; the extraction temperature of a hot rolling heating furnace is 1180-1200 ℃, the furnace time is controlled to be less than 240min, and the plate blank is reheated through hot rolling; firstly, carrying out rough rolling on a casting blank with the thickness of 220mm for 3 times to obtain an initial blank with the thickness of 180-185 mm, carrying out surface confirmation on the initial blank with the thickness of 180-185 mm, and grinding generated cracks; carrying out secondary hot rolling after grinding the primary blank, rolling the primary blank with the thickness of 180-185 mm into a coiled material with the thickness of 4.0-6.0 mm, in order to ensure that no cracks occur on the surface of a steel plate, carrying out 9-pass rolling on the primary blank, namely carrying out multi-pass low reduction rate, rolling the primary blank into the coiled material with the thickness of 23-26 mm before finish rolling, rolling the coiled material with the thickness of 3.5-5.0 mm by 7-pass rolling, and carrying out rapid cooling by using laminar cooling water during coiling, wherein the supercooled austenite of the steel type is continuously cooled to have a transformation curve, and the martensite transformation temperature (Ms) during rapid cooling is low, so that the martensite produced by phase transformation during cooling is less, and the plate shape;
C. annealing and pickling: the steel plate temperature is 1050-1090 ℃ during thermal annealing and pickling, and the production line speed is 10-15 mpm;
D. cold rolling: the primary reduction rate is less than or equal to 40%, and 9-11 passes are adopted in the rolling pass;
E. cold rolling, annealing and pickling: the cold rolling and annealing solid solution temperature is 1020-1070 ℃, when the solid solution temperature is too high, alloy carbides are excessively dissolved into austenite, the stability of the austenite is increased, the martensite formation after cooling is reduced, the strength is reduced after precipitation hardening treatment, and the later stage of the product with too high strength is difficult to process when the solid solution temperature is too low, so that the later stage precipitation hardening treatment performance is greatly influenced by selecting a proper solid solution process;
F. leveling, wherein the steel grade is a martensite phase transformation steel grade, the martensite phase transformation temperature is actually 80-95 ℃, and the product is easy to generate phase transformation in the production process; due to uneven phase change and uneven distribution of precipitated phases, volume change is uneven, residual stress occurs in the tissue, and poor flatness is caused; therefore, the product after the solution treatment is leveled by leveling equipment, and the corresponding flatness is achieved according to the application;
G. and (3) aging, wherein the flat steel plate is aged at the heating temperature of 500-530 ℃, the heating time is more than or equal to 24Hrs, and the high-strength stainless steel plate with the yield strength of 1480-1600 Mpa can be obtained after air cooling to the room temperature.
Test example
FIG. 1 is a graph showing the yield strength and hardness after precipitation hardening simulation aging treatment in examples 1, 2 and 3, and it can be seen that the yield strength and hardness reach maximum values when precipitation hardening treatment is performed at a precipitation hardening treatment temperature of 480 to 500 ℃ after heat preservation for 24hrs (hours).
FIG. 2 is a structure diagram of a metallographic structure of the samples of examples 1, 2 and 3 after precipitation hardening, from which the distribution of precipitated phases can be seen, wherein the precipitated phases are uniformly distributed in the interior of the structure after the precipitation hardening at 480 ℃ and the precipitated phases grow up and are partially dissolved and the strength and hardness are reduced after the precipitation hardening at 530 ℃.
Claims (9)
1. A martensitic precipitation hardening stainless steel, characterized in that the chemical composition of the martensitic precipitation hardening stainless steel comprises, in mass percent: c: 0.04-0.06%; si: 1.4-1.8%; mn: 0.5-0.9%; p: less than or equal to 0.035%; s: less than or equal to 0.008 percent; cr:14 to 14.5 percent; ni: 7-7.8%; 0 to 0.15 percent of Al; 0.55 to 0.7 percent of Mo; cu: 0.7-1.0%; 0 to 0.03 percent of N; 0.28 to 0.35 percent of Ti; the balance of iron and other inevitable impurities; the preparation steps of the martensitic precipitation hardening stainless steel comprise: smelting and continuously casting each raw material of the martensitic precipitation hardening stainless steel, hot rolling, hot annealing and pickling, cold rolling, annealing and pickling, leveling and aging to obtain the martensitic precipitation hardening stainless steel;
wherein, the hot rolling adopts a secondary hot rolling process; the extraction temperature of a hot rolling heating furnace is 1180-1200 ℃, the furnace time is controlled to be less than 240min, and the plate blank is reheated through hot rolling; firstly, carrying out rough rolling on a casting blank with the thickness of 220mm for 3 times to obtain an initial blank with the thickness of 180-185 mm, carrying out surface confirmation on the initial blank with the thickness of 180-185 mm, and grinding generated cracks; carrying out secondary hot rolling after grinding the primary blank, rolling the primary blank with the thickness of 180-185 mm into a coiled material with the thickness of 4.0-6.0 mm, carrying out 9-pass rolling on the primary blank, namely, carrying out multi-pass low reduction rate, entering the coiled material with the thickness of 23-26 mm before finish rolling, rolling the coiled material into the coiled material with the thickness of 3.5-5.0 mm by 7-pass finish rolling, and carrying out quick cooling by using laminar cooling water during coiling;
the aging is carried out after the flattening, the heating temperature is 500-530 ℃, the heating time is more than or equal to 24Hrs, and the high-strength stainless steel plate with the yield strength of 1480-1600 Mpa can be obtained after the air cooling to the room temperature.
2. A martensitic precipitation hardened stainless steel according to claim 1, characterized in that: the smelting and the continuous casting are carried out by an EAF + AOD + VOD + CCP process, VOD adopts a vacuum decarburization technology, vacuum stirring is carried out for 73min, inclusions in steel fully float upwards, and Total [ O ] in the steel is further reduced by using Al deoxidation; in the process of slab Continuous Casting (CCP), the casting speed is preferably not fluctuated to cause the liquid level fluctuation of the crystallizer to cause slag entrapment.
3. A martensitic precipitation hardened stainless steel according to claim 1, characterized in that: the temperature of the steel plate during the thermal annealing and pickling is 1050-1090 ℃, and the production line speed is 10-15 mpm.
4. A martensitic precipitation hardened stainless steel according to claim 1, characterized in that: the primary rolling reduction rate of the cold rolling is less than or equal to 40%, and 9-11 passes are adopted in the rolling pass.
5. A martensitic precipitation hardened stainless steel according to claim 1, characterized in that: the cold rolling annealing solid solution temperature in the cold rolling annealing pickling is 1020-1070 ℃.
6. A martensitic precipitation hardened stainless steel according to claim 1, characterized in that: the flattening is carried out by a leveling device in the process of solution annealing, and the corresponding flatness is achieved according to the application.
7. A martensitic precipitation hardened stainless steel according to any one of claims 1 to 6, characterized in that: the martensite precipitation hardening stainless steel comprises the following chemical components in percentage by mass: c: 0.045%; si: 1.62 percent; mn: 0.72 percent; 0.025 percent of P; 0.0015 percent of S; 14.3 percent of Cr; ni: 7.1 percent; 0.04 to 0.06 percent of Al; 0.65 percent of Mo; cu: 0.82%; 0.01 percent of N; 0.32 percent of Ti; the balance being iron and other unavoidable impurities.
8. A preparation method of martensite precipitation hardening stainless steel is characterized in that raw materials of the martensite precipitation hardening stainless steel are subjected to smelting, continuous casting, hot rolling, thermal annealing and pickling, cold rolling, annealing and pickling, flattening and aging to obtain the martensite precipitation hardening stainless steel; specifically, the method comprises the following steps:
A. smelting and continuous casting: through EAF + AOD + VOD + CCP, VOD adopts vacuum decarburization technology, vacuum stirring is carried out for 73min, inclusions in steel fully float upwards, inclusions in steel are effectively reduced, and Total [ O ] in steel is further reduced by Al deoxidation, so that the formation of non-metallic oxide inclusions is reduced; in the process of slab Continuous Casting (CCP), the casting speed is preferably not to generate speed fluctuation to cause the liquid level fluctuation of a crystallizer to cause slag entrapment;
B. hot rolling: the martensite precipitation hardening stainless steel is sensitive to cracks, and therefore, a secondary hot rolling process is adopted in the design of a rolling process for hot rolling; the extraction temperature of a hot rolling heating furnace is 1180-1200 ℃, the furnace time is controlled to be less than 240min, and the plate blank is reheated through hot rolling; firstly, carrying out rough rolling on a casting blank with the thickness of 220mm for 3 times to obtain an initial blank with the thickness of 180-185 mm, carrying out surface confirmation on the initial blank with the thickness of 180-185 mm, and grinding generated cracks; carrying out secondary hot rolling after grinding the primary blank, rolling the primary blank with the thickness of 180-185 mm into a coiled material with the thickness of 4.0-6.0 mm, carrying out 9-pass rolling on the primary blank in order to ensure that no crack occurs on the surface of a steel plate, rolling the primary blank into the coiled material with the thickness of 23-26 mm before finish rolling, rolling the coiled material with the thickness of 3.5-5.0 mm by 7-pass finish rolling, and carrying out rapid cooling by using laminar cooling water during coiling;
C. annealing and pickling: the steel plate temperature is 1050-1090 ℃ during thermal annealing and pickling, and the production line speed is 10-15 mpm;
D. cold rolling: the primary reduction rate is less than or equal to 40%, and 9-11 passes are adopted in the rolling pass;
E. cold rolling, annealing and pickling: the cold rolling and annealing solid solution temperature is 1020-1070 ℃;
F. leveling, wherein leveling is performed by leveling equipment in solution annealing, and corresponding flatness is achieved according to application;
G. and (4) aging, wherein the flat steel plate is aged at the heating temperature of 500-530 ℃ for more than or equal to 24Hrs, and air-cooled to room temperature to obtain the high-strength stainless steel plate with the yield strength of 1480-1600 Mpa.
9. Use of the martensitic precipitation hardening stainless steel according to any of claims 1-6 in steel strip transmission equipment, moulding equipment.
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| CN112063801A (en) * | 2020-09-17 | 2020-12-11 | 浦项(张家港)不锈钢股份有限公司 | Stainless steel and preparation method thereof |
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| CN112845595A (en) * | 2020-12-31 | 2021-05-28 | 浦项(张家港)不锈钢股份有限公司 | Cold rolling process for titanium-chromium-nickel-containing semi-austenite precipitation hardening stainless steel |
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| CN113215372A (en) * | 2021-04-12 | 2021-08-06 | 太原日德泰兴精密不锈钢股份有限公司 | Production method of stainless steel band for medical clamp |
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| CN113699464A (en) * | 2021-08-25 | 2021-11-26 | 哈尔滨工程大学 | Ultra-high-strength high-performance sheet maraging stainless steel and preparation method thereof |
| CN114395727A (en) * | 2021-12-02 | 2022-04-26 | 浦项(张家港)不锈钢股份有限公司 | Smelting and continuous casting process of martensite precipitation hardening stainless steel |
| CN114737028A (en) * | 2022-04-01 | 2022-07-12 | 山西太钢不锈钢股份有限公司 | Annealing method of precipitation hardening stainless steel |
| CN114737028B (en) * | 2022-04-01 | 2023-03-24 | 山西太钢不锈钢股份有限公司 | Annealing method of precipitation hardening stainless steel |
| CN115341085A (en) * | 2022-07-19 | 2022-11-15 | 常州市联谊特种不锈钢管有限公司 | Manufacturing method of high-strength and high-toughness maraging stainless steel thin-wall seamless pipe |
| CN115341085B (en) * | 2022-07-19 | 2023-10-13 | 常州市联谊特种不锈钢管有限公司 | Manufacturing method of high-strength and high-toughness maraging stainless steel thin-wall seamless pipe |
| CN117551838A (en) * | 2024-01-11 | 2024-02-13 | 成都先进金属材料产业技术研究院股份有限公司 | Control method for low-magnification pocking defects of large-specification martensitic stainless steel forging |
| CN117551838B (en) * | 2024-01-11 | 2024-04-23 | 成都先进金属材料产业技术研究院股份有限公司 | Control method for low-magnification pocking defects of large-specification martensitic stainless steel forging |
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