CN108179360B - Ultra-pure ferrite stainless steel with tin and copper synergistic effect and preparation method thereof - Google Patents
Ultra-pure ferrite stainless steel with tin and copper synergistic effect and preparation method thereof Download PDFInfo
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- CN108179360B CN108179360B CN201810091915.6A CN201810091915A CN108179360B CN 108179360 B CN108179360 B CN 108179360B CN 201810091915 A CN201810091915 A CN 201810091915A CN 108179360 B CN108179360 B CN 108179360B
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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
- C22C38/20—Ferrous alloys, e.g. steel alloys containing chromium with copper
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0205—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips of ferrous alloys
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
- C21D8/0226—Hot rolling
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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
- C22C38/004—Very low carbon steels, i.e. having a carbon content of less than 0,01%
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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
- C22C38/008—Ferrous alloys, e.g. steel alloys containing tin
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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
- C22C38/02—Ferrous alloys, e.g. steel alloys containing 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
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/005—Ferrite
Abstract
The invention relates to an ultra-pure ferritic stainless steel with tin and copper synergistic effect and a preparation method thereof, wherein the ultra-pure ferritic stainless steel comprises the following components in percentage by mass: c is less than or equal to 0.005%, Si: 0.2-0.4%, Mn: 0.2-0.4%, P is less than or equal to 0.005%, S is less than or equal to 0.005%, Cr: 16-18%, N is less than or equal to 0.003%, Sn: 0.095-0.15%, Cu: 0.05-1%, and the balance of Fe and inevitable impurities. The preparation method comprises the following steps: (1) smelting according to set components and casting a casting blank; (2) heating to 1100 +/-10 ℃, preserving heat for 1-2 hours, and then hot rolling to obtain a hot rolled steel plate; (3) the ultra-pure ferrite stainless steel containing tin and copper with synergistic effect is obtained through heat treatment, water cooling, heat preservation and air cooling. According to the method, on the basis of reducing the production cost of the ferritic stainless steel, the mechanical property and the corrosion resistance of the ferritic stainless steel are improved, the tensile strength can reach 450-560 MPa, the elongation is 30-45%, and the pitting potential is 200-285 mV.
Description
Technical Field
The invention belongs to the technical field of stainless steel, and particularly relates to ultra-pure ferrite stainless steel with a tin-copper synergistic effect and a preparation method thereof.
Background
Medium chromium ferritic stainless steels play a very important role in the ferritic stainless steel family. Compared with low-chromium stainless steel, it has better corrosion resistance, and compared with high-chromium stainless steel, it also has excellent formability, so that it is very suitable for industries of household appliances, kitchen and bathroom products, etc. which have certain requirements on corrosion resistance and formability. In recent years, with the development of smelting technology, the C, N content in ferritic stainless steel is greatly reduced, and a series of ultrapure ferritic stainless steel is developed, so that the defects and shortcomings of the traditional ferritic stainless steel are greatly overcome. Meanwhile, with the fluctuation of international nickel value, the cost advantage of the ferritic stainless steel is more prominent. Therefore, due to the advantages of cost, price and performance, the medium-chromium ultra-pure ferritic stainless steel has huge use and development space in the market.
For the steel grades in general, tin is present in the steel as a harmful impurity element, which adversely affects the workability of the steel. The thermal expansion coefficient of tin is greatly different from that of the matrix, and during hot processing, due to the difference of the expansion coefficients, a shear stress field is generated around the tin element to cause mosaic stress, so that cracks are generated on the interface of the tin element and the matrix phase or the effect of early cracks on steel is accelerated. Meanwhile, copper in steel increases the hot brittleness tendency of steel, and deteriorates the hot workability of steel. The root cause of the copper brittleness defect generated in the copper-containing steel is selective oxidation at high temperature to cause copper enrichment, the enriched copper is easily distributed and diffused along the grain boundary because of high lattice mismatching degree at the grain boundary, and the copper brittleness is caused when the grain boundary of the copper-rich layer begins to melt at about 1150 ℃.
The Chinese patent application with the publication number of CN 102690994A, named as a medium chromium ferrite stainless steel and a manufacturing method thereof, discloses a medium chromium ferrite stainless steel, which adopts a continuous annealing mode to replace bell-type furnace annealing to obtain a finished product steel with good formability and crease resistance, optimizes the production process and improves the product quality, and the steel comprises the following chemical components in percentage by mass: c: 0.010-0.030 percent of Si, less than or equal to 0.010 percent of S, less than or equal to 0.035 percent of P, Si: 0.30-1.0%, Mn is less than or equal to 0.30%, Cr: 16.0-18.0%, N: 0.010-0.030%, Ti: 0.1-0.3%, V: 0-0.3%, Nb: 0-0.3 percent, Ti% + Nb% + V% ≥ 2 × (C% + N%), Si% ≥ 2 × Mn%, and the balance iron and inevitable impurities. The invention improves the tensile strength of the steel material by 400-350 MPa, the yield strength by 200-350MPa and the elongation by 20-40 percent, adds the elements V, Ti and Nb in the stainless steel and has higher cost. The corrosion resistance is not studied, which limits the application range of the steel. Meanwhile, the corrosion resistance of steel is not mentioned, and the corrosion resistance of the material meeting the requirements in smelting steel is difficult to ensure.
Chinese patent application with Chinese patent publication No. CN 104736734B, entitled ferritic stainless Steel and method of manufacturing the same, discloses an iron having corrosion resistance of at least a certain level and having tempering color removal of at least a certain levelA ferritic stainless steel and a method for producing the same, wherein the steel comprises the following chemical components (in mass percent): 0.001 to 0.030 wt% of C, 0.03 to 0.30% of Si, 0.05% or less of P, 0.01% or less of S, more than 22.0% and 28.0% or less of Cr, 0.2 to 3.0% of Mo, 0.01 to 0.15% of Al, more than 0.30% and 0.80% or less of Ti, 0.001 to 0.080% of V, and 0.001 to 0.050% of N, further containing 0.05 to 0.30% of Mn and 0.01 to 5.00% of Ni, or containing 0.05 to 2.00% of Mn and 0.01 to 0.30% of Ni, further containing 0.05% or less of Nb as an optional component, and the balance Fe and unavoidable impurities, and having a ratio of 30/mm on the surface2TiN with a particle size of 1 μm or more is distributed in the above density. The ferritic stainless steel has excellent corrosion resistance and excellent removal performance of tempering color, wherein the steel is used for a water storage tank body of an electric water heater, but the application range of the steel is limited because the mechanical property and the processing formability of the steel are not mentioned, and the steel has higher cost and more types of added elements and is difficult to ensure the yield in the smelting process because Mo and V are added into the steel and the Cr content is very high.
Disclosure of Invention
Technical problem to be solved
In order to solve the problems in the prior art, the invention provides the ultra-pure ferritic stainless steel with the synergistic effect of tin and copper and the preparation method thereof.
(II) technical scheme
In order to achieve the purpose, the invention adopts the main technical scheme that:
an ultra-pure ferrite stainless steel with tin and copper synergistic effect comprises the following components by mass percent of less than or equal to 0.005 percent of C, Si: 0.2-0.4%, Mn: 0.2-0.4%, P is less than or equal to 0.005%, S is less than or equal to 0.005%, Cr: 16-18%, N is less than or equal to 0.003%, Sn: 0.095-0.15%, Cu: 0.05-1%, and the balance of Fe and inevitable impurities.
A preparation method of ultra-pure ferritic stainless steel with tin and copper synergistic effect comprises the following steps:
s1, smelting and casting a casting blank, wherein the casting blank comprises the following components in percentage by mass: c is less than or equal to 0.005%, Si: 0.2-0.4%, Mn: 0.2-0.4%, P is less than or equal to 0.005%, S is less than or equal to 0.005%, Cr: 16-18%, N is less than or equal to 0.003%, Sn: 0.095-0.15%, Cu: 0.05-1%, and the balance of Fe and inevitable impurities;
s2, cooling the casting blank to room temperature, heating to 1100 +/-10 ℃, preserving heat for 1-2 hours, and rolling into a hot rolled steel plate through 6-7 times of hot rolling;
and S3, carrying out heat treatment, water cooling, heat preservation and air cooling on the hot-rolled steel plate obtained in the step S2 to obtain the ultra-pure ferritic stainless steel with the synergistic effect of tin and copper.
In the above production method, preferably, the Sn and Cu may be derived from scrap steel.
In the above production method, in step S2, the hot rolling is preferably performed at a start rolling temperature of 1050 to 1100 ℃, a finish rolling temperature of 800 to 850 ℃, and a rolling deformation of 20 to 30%.
In the method for manufacturing the ultrapure ferritic stainless steel, preferably, in step S3, the heat treatment is performed at 1100 ± 10 ℃ for 5-10 min.
In the preparation method of the ultrapure ferritic stainless steel, preferably, in step S3, the heat preservation is 800 ± 10 ℃ for 5-10 min.
Wherein 1100 +/-10 ℃ is in the range of 1090-1110 ℃, and 800 +/-10 ℃ is in the range of 790-810 ℃.
The ultrapure ferritic stainless steel provided by the invention comprises the following components:
carbon: carbon is used as an interstitial element in steel, the content of carbon in ferritic stainless steel is generally less than 0.15%, the content of carbon in ultrapure ferritic stainless steel is less than 0.02%, and the content of carbon is less than 0.005%, so that the phenomenon that the content of carbon is too high, carbon can form a compound with chromium at a grain boundary, and the corrosion resistance of the grain boundary is reduced.
Nitrogen: the nitrogen content is set below 0.003%, so that nitrogen is prevented from precipitating in grain boundaries and forming compounds with chromium, and the corrosion resistance and the processability of the grain boundaries are reduced.
Silicon: the silicon is used for improving the mechanical property of the steel, increasing the strength and simultaneously improving the hardness, the effect of the silicon is second to phosphorus, and the silicon in the invention is set to be 0.2-0.4%. When the ultrapure ferrite stainless steel is oxidized at a higher temperature, Si is oxidized at the same time, and a layer of oxidation film is formed on the surface of the steel, so that the oxidation resistance of the steel is improved. However, when the silicon content exceeds 0.4%, ductility and weldability deteriorate.
Manganese: manganese has a deoxidizing effect and is a good deoxidizing agent and a good desulfurizing agent. The manganese content is set to 0.2-0.4% in the present invention, which is used to eliminate or reduce hot brittleness of steel caused by sulfur, thereby improving hot workability of steel. Manganese and iron form a solid solution, which improves the strength and hardness of the steel. When the Mn content in the steel exceeds 0.4%, precipitation and coarsening of MnS are promoted to cause a decrease in corrosion resistance, and the smelting cost increases.
Phosphorus: although phosphorus can increase the strength and hardness of steel, in the present invention, the content of phosphorus is controlled to 0.005% or less, so that too high phosphorus deteriorates the corrosion resistance of steel, and also deteriorates workability due to segregation, and phosphorus adversely affects weldability.
Sulfur: the sulfur is seriously segregated in the steel, which affects the quality of the steel. In the present invention, the sulfur content is controlled to 0.005% or less, and formation of MnS precipitates from S and Mn is avoided. Such inclusions are sources of pitting corrosion of stainless steel, reducing the corrosion resistance of the steel.
Chromium: chromium is a main component of ferritic stainless steel, and is an important element for determining corrosion resistance and workability of ferritic stainless steel. In the present invention, the chromium content is adjusted within a specific range, which is 16% to 18%. The corrosion resistance of the steel increases with the higher chromium content in the steel, by forming a passive film on the steel surface by chromium to prevent the matrix from being corroded. However, if the Cr content exceeds 18%, the toughness of the steel sheet is lowered, and the steel is excessively hardened, and the elongation of the steel sheet is also significantly lowered, whereas if the Cr content is less than 16%, a steel sheet having sufficient corrosion resistance cannot be obtained.
Copper: in the present invention, the copper content is controlled to 0.05 to 1%, and copper is added to steel as an alloying element for improving corrosion resistance of steel and improving strength and cold workability of steel, but when the Cu content is too high, toughness of steel is lowered and workability is lowered.
Tin: in the invention, the content of tin is controlled to be 0.095-0.15%, and tin is used for improving a surface passivation film structure to improve the pitting corrosion resistance of steel, but when the content of the element is too high, the effect is saturated, and the processability is reduced.
(III) advantageous effects
The invention has the beneficial effects that:
the ultra-pure ferritic stainless steel with the tin and copper synergistic effect, provided by the invention, has the advantages of enhancing the advantages and avoiding the disadvantages by adding tin and copper alloy elements with appropriate content and combining a certain heat treatment process, plays the beneficial effects of tin and copper in steel, has excellent corrosion resistance, has more excellent processing performance compared with 430 ferritic stainless steel in the prior art, and has the advantages of tensile strength of 450-560 MPa, pitting potential of 200-285 mV and elongation after fracture of 30-45%.
Compared with the existing 430-element stainless steel, the invention has the following remarkable advantages:
(1) the invention can obviously reduce the production cost of stainless steel, the accumulation of tin and copper elements exists in the recycling process of the scrap steel, the addition of alloy elements tin and copper can be reduced by adopting the scrap steel as a raw material, in addition, the most important aspect is to reduce the removal process of residual tin and copper elements in the field industrial production, optimize the process production and improve the efficiency. Due to the synergistic effect of tin and copper, the addition of noble metals of nickel and molybdenum can be reduced, the cost is saved, the corrosion resistance of the alloy can be further improved, and the mechanical property is improved to a certain extent (the national standard tensile strength of the steel number 00Cr17 is 365MPa, the elongation is 22%, the tensile strength of the steel is 450-560 MPa, and the elongation is 30-45%). The invention ensures that the processing formability of the steel is above the performance of 430 ferrite stainless steel, greatly improves the corrosion resistance, enlarges the application range and improves the competitiveness of enterprises.
(2) The product has good corrosion resistance, the pitting potential of the product is 200-285 mV, and the corrosion resistance of the product is greatly improved compared with that of 430 ferrite stainless steel (the pitting point is 178mV) without tin and copper elements; meanwhile, the product has good mechanical properties, the tensile strength of the stainless steel is 450-560 MPa, the elongation is 30-45%, and compared with the steel number 00Cr17 national standard, the mechanical index properties are improved, and various deep processing requirements in the application range can be met.
(3) The production process of the product is simple and efficient, the yield of tin and copper added as alloy elements in the steel is over 90 percent, the control is easy, and the product has higher strength, plasticity and corrosion resistance after heat treatment.
Drawings
FIG. 1 is a graph of anodic polarization of tin-copper containing ultra pure ferritic stainless steel;
FIG. 2 is a graph of the effect of copper content on tensile strength and elongation of tin-copper containing ultra pure ferritic stainless steel;
FIG. 3 is a narrow band scan of Sn elements in XPS analysis of a passivating film of tin-copper containing ultrapure ferritic stainless steel;
FIG. 4 is a scanning electron microscope image of the redeposition of copper particles in pitting pits after anodic polarization reaction of tin-copper containing ultra-pure ferritic stainless steel, illustrating the redeposition of copper particles in the field of view;
FIG. 5 is a scanning electron microscope image of the redeposition of copper particles in pitting pits after anodic polarization reaction of tin-copper containing ultra-pure ferritic stainless steel, and the image is the surface scanning result of copper element in the visual field.
Detailed Description
The invention prepares the tin-copper alloying ultrapure ferrite stainless steel by adjusting the components of the stainless steel and carrying out hot rolling, annealing and heat treatment, thereby reducing the production cost of the stainless steel, greatly saving resources such as chromium, nickel and the like, and simultaneously improving the corrosion resistance and the processing formability of the stainless steel. The tin-copper containing ultrapure ferrite stainless steel is high-purity ferrite stainless steel with extremely low carbon and nitrogen contents, has few defects and belongs to body-centered cubic lattices. The internal defects of the high-purity ferritic stainless steel are few, and the body-centered cubic lattice can uniformly disperse tin in the material, so that the problem that the tin is easily broken when being dispersed in the material is completely solved. Meanwhile, the addition of tin causes certain lattice distortion of the ferritic stainless steel, and the tensile strength of the steel is enhanced through solid solution strengthening. In addition, the property of the surface corrosion-resistant film layer can be changed due to the modification effect of tin on the passive film in the stainless steel, so that the passive film is more compact, the Vicat current density is reduced, the tin plays a role of activating a cathode in the atmosphere, the steel can be promoted to generate anodic passivation under certain conditions, and the corrosion rate of the steel is reduced.
The tin-copper containing ultra-pure ferrite stainless steel designed by the invention avoids the copper brittleness temperature through a certain heat treatment process, and can effectively avoid the copper brittleness phenomenon. Meanwhile, the strength of the steel can be greatly improved by copper, and the strength of the experimental steel can be obviously improved by solid-solution copper and copper-rich precipitated phases after aging treatment. In addition, compared with austenitic stainless steel, ferritic stainless steel has unobvious pitting corrosion resistance, so that the application range of the ferritic stainless steel is greatly restricted, but the corrosion resistance of the designed steel can be improved by adding a proper amount of copper. In the pitting development process, the copper-containing ions in the pitting pits can generate a redeposition phenomenon of Cu particles and deposit on the metal surface, so that the matrix is passivated, the anodic dissolution is inhibited, and the pitting corrosion of the steel is effectively hindered.
The tin and copper in the invention have synergistic effect: the tin-copper synergistic effect is that tin and copper elements act together to improve the corrosion resistance as the name suggests. The specific action mechanism is as follows: tin generates compact SnO on the surface of steel in the corrosion process2The passive film (shown in figure 3) effectively prevents the interaction of the matrix and a corrosion medium, and inhibits the corrosion of the steel in the medium. While copper is enriched on the surface of the steel in the corrosion process in the mode of redepositing particles (as shown in figure 4), the deposited particles passivate the steel matrix and reduce the dissolution speed of the steel.
For the purpose of better explaining the present invention and to facilitate understanding, the present invention will be described in detail by way of specific embodiments with reference to the accompanying drawings.
Smelting and casting a casting blank according to set components, wherein the smelting is performed by adopting an electric furnace or a converter, VOD refining and LF refining, and the casting is performed by adopting slab continuous casting; or smelting directly through a vacuum induction furnace, wherein the casting is die casting or slab continuous casting.
The standard GB/T228-2002 is adopted for testing the tensile strength in the embodiment of the invention, a rolled sample is cut into room-temperature tensile samples with the gauge length of 50mm and the width of 12.5mm by a numerical control wire cutting machine, quenching and tempering heat treatment processes (the quenching temperature is 1100 ℃, the heat preservation time is 5min, water cooling, the tempering temperature is 800 ℃, the heat preservation time is 5min, air cooling) are respectively carried out, and then a room-temperature tensile experiment is carried out on an INSTRON-4206 electronic universal testing machine.
In the embodiment of the invention, the pitting potential is tested by cutting a prepared stainless steel plate into steel samples of 10.5mm multiplied by 10.5mm in a linear manner, respectively carrying out quenching and tempering heat treatment processes (quenching temperature is 1100 ℃, heat preservation time is 5min, water quenching, tempering temperature is 800 ℃, heat preservation time is 5min, air cooling), and wet-grinding the heat-treated samples on No. 240, No. 400, No. 600 and No. 800 sand paper to 800 meshes in sequence. To prevent crevice corrosion, the ground sample was passivated (50 ℃ C., 50% HNO)3Soak for 1 hour). Reserve 1cm2After a copper wire is welded on a working area of a test sample, the other surfaces except the working surface are coated with epoxy resin to seal the test sample, then the test sample is continuously wet-milled on 800#, 1000#, 1200#, 1500# and 2000# abrasive paper in sequence until the scratches are consistent, and the test sample is cleaned by deionized water and absolute ethyl alcohol and dried for standby. And (3) selecting an electrochemical method, and measuring the cathodic and anodic polarization curves of the sample to be measured by potentiodynamic according to a GB/T17899-19999 stainless steel pitting potential measuring method through a Gamry (Reference600) electrochemical workstation in the United states to obtain the pitting potential of the stainless steel.
In the embodiment of the invention, the standard for testing the elongation after fracture is GB/T228-2002, a rolled sample is cut into room-temperature tensile samples with the gauge length of 50mm and the width of 12.5mm by a numerical control wire cutting machine, quenching and tempering heat treatment processes (the quenching temperature is 1100 ℃, the heat preservation time is 5min, water quenching, the tempering temperature is 800 ℃, the heat preservation time is 5min, air cooling) are respectively carried out, and then a room-temperature tensile experiment is carried out on an INSTRON-4206 electronic universal testing machine.
Example 1
Preparation of tin-copper containing ultra pure ferritic stainless steel:
(1) smelting and casting a casting blank according to set components, wherein the mass percentage of each component is as follows: 0.069%, Sn: 0.096%, Cr: 17.84%, C: 0.004%, Si: 0.25%, Mn: 0.32%, P: 0.0048%, S: 0.0048%, N: 0.0028%, the balance being iron and unavoidable impurities.
(2) Cooling the casting blank to room temperature, reheating to 1100 ℃, preserving heat for 2h, rolling by using a 450mm hot rolling unit testing machine, wherein the initial rolling temperature is 1100 ℃, the final rolling temperature is 850 ℃, the deformation amount of single rolling is controlled at 25%, and the thickness of the plate finally rolled and formed through 7-pass rolling is 3 mm.
(3) Carrying out quenching and tempering heat treatment on the hot rolled steel plate, wherein the quenching temperature is 1100 ℃, the heat preservation time is 5min, and water cooling; tempering temperature is 800 ℃, heat preservation time is 5min, and air cooling is carried out to obtain the tin-copper containing alloyed ultra-pure ferrite stainless steel; tensile strength 461MPa, pitting potential 195.5mV, and elongation after fracture 37%.
Example 2
Preparation of tin-copper containing ultra pure ferritic stainless steel:
(1) smelting and casting a casting blank according to set components, wherein the mass percentage of each component is as follows: 0.13%, Sn: 0.096%, Cr: 17.40%, C: 0.004%, Si: 0.29%, Mn: 0.32%, P: 0.0049%, S: 0.004%, N: 0.0025%, the balance being iron and unavoidable impurities.
(2) Cooling the casting blank to room temperature, reheating to 1110 ℃, preserving heat for 1.5h, rolling by using a 450mm hot rolling unit testing machine, wherein the initial rolling temperature is 1050 ℃, the final rolling temperature is 850 ℃, the deformation amount of single rolling is controlled at 25%, and the thickness of the plate finally rolled and formed through 7-pass rolling is 3 mm.
(3) Carrying out quenching and tempering heat treatment on the hot rolled steel plate, wherein the quenching temperature is 1095 ℃, the heat preservation time is 8min, and water cooling; tempering at 795 ℃, keeping the temperature for 10min, and air cooling to obtain the tin-copper-containing alloyed ultra-pure ferritic stainless steel; 487MPa tensile strength, 234.8mV pitting potential and 39% elongation after fracture.
Example 3
(1) Smelting and casting a casting blank according to set components, wherein the mass percentage of each component is as follows: 0.20%, Sn: 0.10%, Cr: 17.34%, C: 0.005%, Si: 0.25%, Mn: 0.31%, P: 0.0042%, S: 0.0045%, N: 0.002%, and the balance of iron and unavoidable impurities.
(2) Cooling the casting blank to room temperature, reheating to 1090 ℃, preserving heat for 2 hours, rolling by using a 450mm hot rolling unit testing machine, wherein the initial rolling temperature is selected to be 1070 ℃, the final rolling temperature is 850 ℃, the deformation amount of single rolling is controlled to be 20%, and the thickness of the plate finally rolled and formed through 7-pass rolling is 3 mm.
(3) Carrying out quenching and tempering heat treatment process (quenching temperature 1110 ℃, heat preservation time 5min, water cooling, tempering temperature 805 ℃, heat preservation time 7min, air cooling) on the hot rolled steel plate to obtain the tin-copper containing alloyed ultra-pure ferritic stainless steel; the tensile strength is 493MPa, the pitting potential is 273.2mV, and the elongation after fracture is 41.5%.
Example 4
Preparation of tin-copper containing ultra pure ferritic stainless steel:
(1) smelting and casting a casting blank according to set components, wherein the mass percentage of each component is as follows: 0.36%, Sn: 0.098%, Cr: 17.69%, C: 0.005%, Si: 0.25%, Mn: 0.31%, P: 0.004%, S: 0.0042%, N: 0.0021% and the balance iron and unavoidable impurities.
(2) Cooling the casting blank to room temperature, reheating to 1105 ℃, preserving heat for 1h, rolling by using a 450mm hot rolling unit testing machine, wherein the initial rolling temperature is 1080 ℃, the final rolling temperature is 830 ℃, the deformation amount of single rolling is controlled at 20%, and the thickness of the plate finally rolled and formed through 6-pass rolling is 3 mm.
(3) Carrying out quenching and tempering heat treatment on the hot rolled steel plate, wherein the quenching temperature is 1090 ℃, the heat preservation time is 10min, and water cooling is carried out; tempering temperature is 850 ℃, heat preservation time is 5min, and air cooling is carried out to obtain the tin-copper containing alloyed ultra-pure ferrite stainless steel; tensile strength of 523MPa, pitting potential of 285.6mV, and elongation after fracture of 45%.
Example 5
Preparation of tin-copper containing ultra pure ferritic stainless steel:
(1) smelting and casting a casting blank according to set components, wherein the mass percentage of each component is as follows: 1.0%, Sn: 0.15%, Cr: 17.57%, C: 0.005%, Si: 0.27%, Mn: 0.32%, P: 0.0041%, S: 0.0046%, N: 0.0023%, the balance being iron and unavoidable impurities.
(2) And cooling the casting blank to room temperature, reheating to 1100 ℃, preserving heat for 2h, rolling by using a 450mm hot rolling unit testing machine, wherein the initial rolling temperature is 1090 ℃, the final rolling temperature is 850 ℃, the deformation amount of single rolling is controlled at 25%, and the thickness of the plate finally rolled and formed through 7-pass rolling is 3 mm.
(3) Carrying out quenching and tempering heat treatment process (the quenching temperature is 1100 ℃, the heat preservation time is 5min, water cooling, the tempering temperature is 800 ℃, the heat preservation time is 5min, air cooling) on the hot rolled steel plate to obtain the tin-copper containing alloyed ultra-pure ferritic stainless steel; tensile strength 560MPa, pitting potential 170.8mV, and elongation after fracture 35.5%.
Comparative example
Preparation of 430 ferritic stainless steel: (the components are carried out according to the national standard range of 430 ferritic stainless steel)
(1) Smelting and casting a casting blank according to set components, wherein the mass percentage of each component is as follows: 17.41%, C: 0.004%, Si: 0.26%, Mn: 0.31%, P: 0.0057%, S: 0.0051%, N: 0.0053%, and the balance of iron and unavoidable impurities.
(2) Cooling the casting blank to room temperature, reheating to 1100 ℃, preserving heat for 2h, rolling by using a 450mm hot rolling unit testing machine, wherein the initial rolling temperature is 1100 ℃, the final rolling temperature is 850 ℃, the deformation amount of single rolling is controlled at 25%, and the thickness of the plate finally rolled and formed through 7-pass rolling is 3 mm.
(3) Carrying out quenching and tempering heat treatment on the hot rolled steel plate, wherein the quenching temperature is 1100 ℃, the heat preservation time is 5min, and water cooling; tempering temperature is 800 ℃, heat preservation time is 5min, and air cooling is carried out to obtain 430 ferrite stainless steel; the tensile strength is 413MPa, the pitting potential is 178.8mV, and the elongation after fracture is 35.5%.
The pitting potentials measured by anodizing the stainless steels prepared in the examples are plotted in the same graph according to different copper contents, as shown in fig. 1, the results show that the pitting potentials of the tin-copper-containing ultra-pure ferritic stainless steels are increased and then decreased along with the increase of the copper content, and the pitting potential is highest when the Cu content is 0.35%, which indicates that the appropriate copper content exists and the pitting corrosion resistance is reduced due to excessive copper.
The tensile strength and elongation measured for the stainless steels prepared in the examples are plotted in the same graph, as shown in fig. 2, and the results show that the tensile strength of the tin-copper containing ultrapure ferritic stainless steel increases with the increase of the copper content, but the elongation increases and then decreases, and the comprehensive mechanical property is optimal when the Cu content is 0.35% in consideration of the comprehensive mechanical property requirement.
Taking a narrow-band scanning map of Sn element in XPS analysis of the passivation film of tin-copper-containing ultrapure ferritic stainless steel prepared in example 4 as an example, the Cu content is 0.36%, as shown in FIG. 3, it can be seen from XPS analysis that tin is mainly SnO in the passivation film on the steel surface2The corrosion inhibitor can effectively prevent the interaction of a matrix and a corrosion medium and inhibit the corrosion of steel in the medium.
Taking the tin-copper-containing ultrapure ferritic stainless steel prepared in example 4 as an example, as shown in fig. 4 and 5, scanning electron microscope images of redeposition phenomenon of copper particles in pitting pits after anodic polarization reaction of the tin-copper-containing ultrapure ferritic stainless steel and surface scanning results of copper elements are shown, it can be known from the images that the copper elements can be enriched on the surface of the steel in a redeposition particle mode in the pitting corrosion process, the main component of the deposited particles is Cu, the redeposition particles cover the surface of the pitting pits, the steel matrix is passivated, and the dissolution rate of the steel is reduced, thereby improving the pitting corrosion resistance.
The foregoing is directed to the preferred embodiment of the present invention and is not intended to be exhaustive or to limit the invention to the precise form disclosed. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are within the protection scope of the technical solution of the present invention.
Claims (2)
1. The ultra-pure ferritic stainless steel with the tin and copper synergistic effect is characterized by comprising the following components in percentage by mass of less than or equal to 0.005% of C, Si: 0.2-0.4%, Mn: 0.2-0.4%, P is less than or equal to 0.005%, S is less than or equal to 0.005%, Cr: 16-18%, N is less than or equal to 0.003%, Sn: 0.095-0.15%, Cu: 0.13-0.36%, and the balance of Fe and inevitable impurities.
2. A preparation method of ultra-pure ferritic stainless steel with tin and copper synergistic effect is characterized by comprising the following steps:
s1, smelting and casting a casting blank, wherein the casting blank comprises the following components in percentage by mass, C is less than or equal to 0.005%, and Si: 0.2-0.4%, Mn: 0.2-0.4%, P is less than or equal to 0.005%, S is less than or equal to 0.005%, Cr: 16-18%, N is less than or equal to 0.003%, Sn: 0.095-0.15%, Cu: 0.13-0.36% and the balance of iron;
s2, cooling the casting blank to room temperature, heating to 1100 +/-10 ℃, preserving heat for 1-2 hours, and carrying out hot rolling for 6-7 times, wherein the initial rolling temperature of the hot rolling is 1050-1100 ℃, the final rolling temperature is 800-850 ℃, and the rolling deformation is 20-30%; rolling to obtain a hot rolled steel plate;
s3, carrying out heat treatment, water cooling, heat preservation and air cooling on the hot-rolled steel plate obtained in the step S2 to obtain the ultra-pure ferritic stainless steel with the synergistic effect of tin and copper;
the heat treatment is to keep the temperature at 1100 +/-10 ℃ for 5-10 min;
in step S3, the temperature is maintained at 800 +/-10 ℃ for 5-10 min.
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