CN105821299B - High-corrosion-resistance antibacterial ferritic stainless steel and manufacturing method thereof - Google Patents
High-corrosion-resistance antibacterial ferritic stainless steel and manufacturing method thereof Download PDFInfo
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- 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
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- 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
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- 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
- C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
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- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/28—Ferrous alloys, e.g. steel alloys containing chromium with titanium or zirconium
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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
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Abstract
A high corrosion resistance antibacterial ferrite stainless steel and a manufacturing method thereof are disclosed, wherein the chemical components by weight percentage are as follows: less than or equal to 0.015 percent of C, Si: 0.1 to 0.5%, Mn: 0.1-0.5%, P is less than or equal to 0.035%, S is less than or equal to 0.010%, Cr: 18-22%, Mo: 0.5 to 1.0%, Cu: 1.5-2.5%, N: 0.015-0.020%, not more than 8(C + N) and not more than 0.5% of Ti, and the balance of Fe and inevitable impurities. The ferritic stainless steel is smelted by an electric arc furnace, AOD and VOD three-step method, a continuous casting blank is obtained after continuous casting, and then the cold-rolled stainless steel strip with good corrosion resistance and antibacterial performance is obtained through hot-rolling high-temperature direct quenching, hot-rolled strip steel annealing and pickling, cold rolling, annealing and pickling and the like, wherein the pitting point position of the steel is 0.25-0.35V.
Description
Technical Field
The present invention relates to a stainless steel and a method for manufacturing the same, and more particularly, to a highly corrosion-resistant antibacterial ferritic stainless steel having not only antibacterial properties but also excellent corrosion resistance, and a method for manufacturing the same.
Background
The antibacterial ferritic stainless steel has good workability and antibacterial performance, and generally, metal elements with antibacterial action are added in the smelting process of steel to form an antibacterial phase in the steel so as to make the whole stainless steel have antibacterial property. The basic principle of the copper-containing antibacterial stainless steel is that the change of the solid solubility of copper in the steel along with the temperature is utilized, the aging treatment is carried out after the solid solubility, and the precipitated copper-rich phase endows the material with an antibacterial function.
The existing commercial copper-containing ferritic antibacterial stainless steel is generally added with 2 percent of Cu on the basis of 430 ferritic stainless steel, and the purpose of precipitating a copper-rich phase on a ferritic matrix can be realized by adopting the same production process as 430 ferritic stainless steel. However, the 430-class antibacterial steel has high carbon content (generally 0.03-0.05% of C), and a large amount of carbide and copper-rich phases exist on a ferrite matrix, so that the corrosion resistance is reduced, and the requirements of industries such as kitchens and bathrooms, household appliances, medicines and the like on the corrosion resistance of stainless steel are difficult to meet.
The ultra-pure ferritic stainless steel adopts ultra-low C, and a certain amount of Cr and Mo and stabilizing elements Nb and Ti are added, so that the ultra-pure ferritic stainless steel has good corrosion resistance. But because Nb and Ti alloy elements are added, the recrystallization annealing temperature of the ferritic stainless steel is increased to 900-1000 ℃. In the case of ultra pure ferritic stainless steel with copper added, the copper-rich phase precipitated by aging treatment dissolves at such high annealing temperatures, resulting in the disappearance of the antibacterial properties. Therefore, how to solve the matching of the recrystallization annealing temperature and the copper-rich phase dissolution temperature of the stabilized ultrapure ferritic stainless steel is the key for developing the antibacterial stainless steel with high corrosion resistance.
Disclosure of Invention
The invention aims to provide high-corrosion-resistance antibacterial ferritic stainless steel and a manufacturing method thereof, the ferritic stainless steel has good antibacterial performance and high corrosion resistance, wherein the point of pitting corrosion can reach 0.25-0.35V.
In order to achieve the purpose, the invention mainly adopts the following technical scheme:
a high corrosion resistance antibacterial ferritic stainless steel comprises the following chemical components in percentage by weight: less than or equal to 0.015 percent of C, Si: 0.1 to 0.5%, Mn: 0.1-0.5%, P is less than or equal to 0.035%, S is less than or equal to 0.010%, Cr: 18-22%, Mo: 0.5 to 1.0%, Cu: 1.5-2.5%, N: 0.015-0.020%, not more than 8(C + N) and not more than 0.5% of Ti, and the balance of Fe and inevitable impurities.
Furthermore, the microstructure of the high-corrosion-resistance antibacterial ferritic stainless steel is a ferrite matrix and a copper-rich phase.
The pitting point position of the high-corrosion-resistance antibacterial ferritic stainless steel is 0.25-0.35V.
In the composition design of the steel of the invention:
cu (copper): the solubility of copper in ferrite is very low, copper-rich phase is precipitated after aging treatment, and copper-rich phase particles grow gradually along with the increase of aging temperature and the extension of aging time. Cu produced by the action of a copper-rich phase with a mediator2+The ions act with bacteria to make them fineThe bacteria lose the ability of reproduction and survival, thereby playing the role of sterilization. The higher the copper content of ferritic stainless steel, the more remarkable the antibacterial effect, but too high a copper content leads to cracks in the hot worked surface. Therefore, the Cu content is controlled to be 1.5-2.5%.
Cr (chromium): chromium is an element that imparts a ferritic structure to stainless steel and has good corrosion resistance. In an oxidizing medium such as air, chromium reacts with oxygen to form dense chromium oxide (Cr)2O3) And (5) passivating the film. The passive film still keeps stable and passive state under the action of the medium, and prevents harmful substances from corroding a stainless steel matrix, so that the stainless steel has good corrosion performance. The higher the chromium content, the better the corrosion resistance. An excessively high chromium content increases the tendency of brittle phases to precipitate, reducing the manufacturability and the processing profile of the steel. In order to ensure that the developed antibacterial ferritic stainless steel has good corrosion resistance and processability, the content of Cr is controlled to be 18-22%.
Mo (molybdenum): molybdenum is a ferrite forming element, so that the pitting corrosion resistance and the crevice corrosion resistance of the stainless steel can be obviously improved, and the strength of the stainless steel can also be improved. However, too high a molybdenum content promotes precipitation of brittle phases, which leads to deterioration of workability, and also increases the stress corrosion sensitivity of the ferritic stainless steel. Therefore, the content of Mo is controlled to be 0.5-1.0%.
Ti (titanium): titanium is the most effective stabilizing element of ferritic stainless steel, nitrogen is a harmful element in the steel, free carbon and nitrogen atoms in the steel are fixed by adding the titanium to form stable TiN and TiC, and the precipitation of chromium nitride and chromium carbide is prevented, so that the intergranular corrosion resistance is improved. According to the solubility product formula of TiN in the ferritic stainless steel, the precipitation temperature of TiN is controlled by adjusting the content of Ti and N, the size and distribution of TiN are adjusted, and the recrystallization temperature of the ferritic stainless steel is further controlled. The larger size of TiN does not hinder the recrystallization of the ferritic stainless steel, so the ferrite recrystallization temperature is not increased; the fine TiN hinders recrystallization, increases the ferrite recrystallization temperature, and when the recrystallization temperature is sufficiently high, causes the copper-rich phase to dissolve, and the antibacterial effect disappears. By controlling the contents of Ti, C and N, TiN with the thickness of 1-2 mu m is precipitated at the solidification front edge, so that fine TiN is not precipitated at the later stage, and the recrystallization annealing temperature can be controlled within the temperature range in which the copper-rich phase is not dissolved. Therefore, in the present invention, control N: 0.015-0.020% and 0.5% of Ti not less than 8(C + N).
C (carbon): carbon is used as a gap element, so that the strength of the ferritic stainless steel can be obviously improved, the ductile-brittle transition temperature can be improved, the notch crack sensitivity can be increased, and the corrosion resistance of a welding line can be reduced; the lower the carbon content, the better the ferritic stainless steel performance, but the carbon is difficult to remove completely during the stainless steel smelting process. Considering practical production, the invention requires that the content of C is controlled below 0.015 percent.
Si (silicon), Mn (manganese): silicon and manganese are necessary elements in steel, and in order to improve the purity of the steel, the silicon and manganese elements are required to be added for deoxidation so as to improve the toughness and the surface quality of the stainless steel. However, too high silicon and manganese contents reduce the plasticity and toughness of the stainless steel and deteriorate cold workability. The invention controls Si to be less than or equal to 0.5 percent and Mn to be less than or equal to 0.5 percent.
P (phosphorus), S (sulfur): phosphorus and sulfur are impurity elements in the stainless steel, and the corrosion resistance and the plasticity of the steel are reduced. Phosphorus and sulfur also reduce the high-temperature plasticity of the stainless steel, thereby causing the quality problems of continuous casting and hot rolling of the stainless steel, such as internal cracks and edge cracks, and the content of the phosphorus and the sulfur should be reduced as much as possible. In consideration of actual production capacity, P is controlled to be less than or equal to 0.035% and S is controlled to be less than or equal to 0.010%.
The invention relates to a method for manufacturing high-corrosion-resistance antibacterial ferritic stainless steel, which comprises the following steps:
1) smelting
Smelting by an electric arc furnace according to the following chemical components in percentage by weight: less than or equal to 0.015 percent of C, less than or equal to 0.5 percent of Si, less than or equal to 0.5 percent of Mn, less than or equal to 0.035 percent of P, less than or equal to 0.010 percent of S, and the weight percentage of Cr: 18-22%, Mo: 0.5 to 1.0%, Cu: 1.5-2.5%, N: 0.015-0.020%, more than or equal to 8(C + N) and less than or equal to 0.5% of Ti, and the balance of Fe and inevitable impurities;
2) continuous casting
The molten steel treated by the VOD furnace is sent to a continuous casting machine for continuous casting to obtain a continuous casting blank, and the continuous casting blank is subjected to hot finishing and grinding treatment;
3) hot rolling, coiling and cooling
Heating the continuous casting slab to 1150-1200 ℃, and carrying out hot rolling after heat preservation for 190-230 min, wherein the final rolling temperature is 850-900 ℃; cooling by a water curtain, coiling at the temperature of 600-650 ℃, and then cooling by water;
4) hot rolling annealing and pickling
The hot rolling annealing temperature is 850-900 ℃, and the hot rolling annealing time is 2-4 h;
5) cold rolling, cold rolling annealing, pickling and flattening
And (3) cold rolling reduction of 60-80%, cold rolling annealing temperature of 850-900 ℃, annealing time per unit thickness of 1-1.5 min/mm, and leveling to obtain the finished product of the ferritic stainless steel.
Further, in the step 1), firstly, the blast furnace molten iron is sent to an electric arc furnace in smelting, high-carbon Cr-Fe alloy is added and heated, stainless steel mother liquor is prepared and sent to an AOD furnace for decarburization, ferromolybdenum alloy is added and sent to a VOD furnace, and after oxidation, reduction and vacuum decarburization, titanium wire feeding is carried out for treatment.
In the invention, the volume fraction of the copper-rich phase is in direct proportion to the concentration of vacancy point defects, and the increase of the concentration of vacancies in the steel is beneficial to the precipitation of the copper-rich phase. And the concentration of vacancy point defects is related to the quenching temperature after high-temperature deformation, and the higher the quenching temperature is, the higher the concentration of vacancies reserved to room temperature is. Therefore, in order to promote the precipitation of the copper-rich phase, the invention adopts a direct quenching process at high temperature after hot rolling, the finishing temperature is controlled at 850-900 ℃, the steel coil is cooled by a water curtain and then coiled, and the steel coil is cooled by water, so that the concentration of vacancy in the steel is improved, and the precipitation nucleation rate of the copper-rich phase is improved.
The method aims at carrying out aging treatment on the steel coil subjected to high-temperature finish rolling quenching at 850-900 ℃ so as to promote the full precipitation of the copper-rich phase. Meanwhile, in order to avoid the dissolution of the copper-rich phase, the invention controls the cold rolling annealing temperature not to exceed 900 ℃.
The invention has the beneficial effects that:
1. according to the invention, on the basis of the antibacterial ferritic stainless steel, C is controlled to be less than or equal to 0.015 percent, and the intergranular corrosion resistance of the antibacterial ferritic stainless steel is improved through the design of ultralow C content; and stable TiN and TiC are formed by adding Ti, thereby preventing the reduction of Cr concentration caused by the formation of Cr carbon nitrogen compound and the reduction of corrosion resistance. The steel has a pitting point position of 0.25-0.35V, better corrosion resistance than 430-class antibacterial steel, and good antibacterial performance, and the sterilization rate of more than 96.5 percent.
2. For the ultra-pure ferrite stainless steel added with Cu, the recrystallization annealing temperature of the steel is greatly improved due to the addition of Nb and Ti, so that the separated copper-rich phase is dissolved at a higher recrystallization annealing temperature, and finally the antibacterial performance disappears. The steel of the invention is not added with Nb, and Ti is controlled to be more than or equal to 8(C + N), thereby ensuring that the recrystallization annealing temperature of the ferritic stainless steel does not exceed the dissolution temperature of the copper-rich phase, and ensuring that the steel still has excellent antibacterial performance.
3. The invention adopts the direct high-temperature quenching process after hot rolling, improves the vacancy concentration in the steel, is beneficial to the dispersion and precipitation of the copper-rich phase and is beneficial to obtaining excellent antibacterial performance.
4. The ferritic stainless steel has good pitting corrosion resistance, intergranular corrosion resistance and good antibacterial performance, and is a ferritic antibacterial material with a good application prospect.
Drawings
FIG. 1 is a photograph of the precipitation morphology of a copper-rich phase after bell-type furnace annealing in example 2 of the present invention.
FIG. 2 is a photograph of the precipitation morphology of the copper-rich phase after the bell-type furnace annealing of comparative example 1.
FIG. 3 is a photograph of the electrochemical etching morphology in example 2 of the present invention.
FIG. 4 is a photograph of the electrochemical etching morphology of comparative example 1.
Detailed Description
The invention is further illustrated by the following examples and figures.
Table 1 shows the compositions of the steels according to the examples of the present invention and the steels according to the comparative examples of the present invention, table 2 shows the key process parameters of the steels according to the examples of the present invention and the steels according to the comparative examples of the present invention, and table 3 shows the results of the pitting potential test and the sterilization rate test of the steels according to the examples of the present invention.
The manufacturing process of the embodiment of the invention is as follows:
1) smelting
According to the chemical composition shown in Table 1Smelting in an electric arc furnace, namely delivering blast furnace molten iron to the electric arc furnace, adding high-carbon Cr-Fe alloy, heating to prepare stainless steel mother liquor, wherein the temperature of the stainless steel mother liquor is more than or equal to 1670 ℃, the carbon content is 2.5-3.5%, delivering the stainless steel mother liquor to an AOD furnace, and adopting Ar and O2Decarbonizing, adding ferromolybdenum alloy, sending to a VOD furnace, oxidizing, reducing, vacuum decarbonizing, and feeding titanium wire.
2) Continuous casting
And (3) sending the molten steel treated by the VOD furnace to a continuous casting machine for continuous casting to obtain a continuous casting blank, carrying out electromagnetic stirring in the continuous casting process, wherein the thickness of the continuous casting blank is 200mm, and carrying out thermal grinding treatment on the continuous casting blank.
3) Hot rolling, coiling and cooling
Heating the continuous casting slab to 1150-1200 ℃, carrying out hot rolling after heat preservation for 190-230 min, wherein the final rolling temperature is 850-; and cooling by a water curtain, and then coiling at the coiling temperature of 600-650 ℃, and then discharging water in a water tank for cooling.
4) Hot rolling annealing and pickling
And the hot rolling annealing temperature is 850-900 ℃, a bell-type furnace is adopted for annealing, and the hot rolling annealing heat preservation time is 2-4 h, so that the copper-rich phase is fully precipitated. And (3) carrying out acid pickling in a continuous acid pickling machine set, wherein the TV value is 100-200 mm multiplied by m/min, and the acid pickling is carried out by adopting mixed acid of nitric acid and hydrofluoric acid through neutral salt electrolysis.
5) Cold rolling, cold rolling annealing, pickling and flattening
The cold rolling reduction is 60-80%, the cold rolling annealing temperature is 850-900 ℃, the TV value of an annealing unit is 20-50 mm multiplied by m/min, mixed acid of nitric acid and hydrofluoric acid is adopted for pickling, and a finished product of ferrite stainless steel is obtained after flattening, wherein the thickness of the steel plate is 0.5-0.8 mm.
The key process parameters of the inventive examples and comparative examples are shown in table 2, and comparative example 1 is a conventional 430-class antibacterial ferritic stainless steel.
FIGS. 1 and 2 show the structure morphology of the bell-type furnace after annealing in example 2 and comparative example 1. As can be seen from FIG. 1, the copper-rich phase is simultaneously precipitated in ferrite crystal and grain boundary under the high-temperature quenching process after hot rolling; as can be seen from fig. 2, Cu is mainly precipitated at grain boundaries under the conventional rolling process.
Table 3 shows the test results of the pitting point positions and the sterilization rates of finished products of the examples and the comparative examples, and as can be seen from Table 3, the pitting point positions of the examples 1-6 are obviously higher than those of the comparative examples 1-6, and the pitting point positions of the stainless steel are 0.25-0.35V, so that the stainless steel reaches the level of 304 stainless steel and 443 stainless steel, and has good antibacterial performance.
FIGS. 3 and 4 are comparison of electrochemical corrosion morphologies of the steel of example 2 and the steel of comparative example 1 under the same electrochemical test conditions. As can be seen from fig. 3 to 4, comparative example 1 has a large pitting and example 2 has no significant pitting under the same electrochemical test conditions, and exhibits good corrosion resistance. Meanwhile, as can be seen from fig. 3 and 4, the copper-rich phase content in example 2 is obviously higher than that in comparative example 1, and the superiority of the hot-rolling high-temperature quenching process of the invention is shown.
As described above, the antibacterial ferritic stainless steel has good corrosion resistance, overcomes the defect of poor corrosion resistance of 430-class antibacterial stainless steel, and can greatly expand the application of the antibacterial ferritic stainless steel.
Claims (4)
1. A high corrosion resistance antibacterial ferritic stainless steel is characterized in that: the weight percentage of the chemical components is as follows: less than or equal to 0.015 percent of C, Si: 0.1 to 0.5%, Mn: 0.1-0.5%, P is less than or equal to 0.035%, S is less than or equal to 0.010%, Cr: 18-22%, Mo: 0.5 to 1.0%, Cu: 1.5-2.5%, N: 0.015-0.020%, more than or equal to 8(C + N) and less than or equal to 0.5% of Ti, and the balance of Fe and inevitable impurities; the manufacturing method of the high-corrosion-resistance antibacterial ferritic stainless steel comprises the following steps:
1) smelting
Smelting the chemical components in an electric arc furnace;
2) continuous casting
The molten steel treated by the VOD furnace is sent to a continuous casting machine for continuous casting to obtain a continuous casting blank, and the continuous casting blank is subjected to hot finishing and grinding treatment;
3) hot rolling, coiling and cooling
Heating the continuous casting slab to 1150-1200 ℃, and carrying out hot rolling after heat preservation for 190-230 min, wherein the final rolling temperature is 850-900 ℃; cooling by a water curtain, coiling at the temperature of 600-650 ℃, and then cooling by water;
4) hot rolling annealing and pickling
The hot rolling annealing temperature is 850-900 ℃, and the hot rolling annealing time is 2-4 h;
5) cold rolling, cold rolling annealing and pickling
And (3) cold rolling reduction of 60-80%, cold rolling annealing temperature of 850-900 ℃, annealing time per unit thickness of 1-1.5 min/mm, and leveling to obtain the finished product of the ferritic stainless steel.
2. The highly corrosion resistant antibacterial ferritic stainless steel according to claim 1, characterized in that the microstructure of the highly corrosion resistant antibacterial ferritic stainless steel is a ferritic matrix + copper rich phase.
3. The highly corrosion-resistant antibacterial ferritic stainless steel according to claim 1 or 2, characterized in that the pitting point of the highly corrosion-resistant antibacterial ferritic stainless steel is 0.25-0.35V.
4. The highly corrosion-resistant antibacterial ferritic stainless steel according to claim 1, characterized in that, in the step 1) smelting process, blast furnace molten iron is sent to an electric arc furnace, high-carbon Cr-Fe alloy is added and heated to prepare stainless steel mother liquor, the stainless steel mother liquor is sent to an AOD furnace for decarburization, ferromolybdenum alloy is added, the stainless steel mother liquor is sent to a VOD furnace, and after oxidation, reduction and vacuum decarburization, titanium wire feeding is carried out.
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